JPH11158189A - Transition metal compound, catalytic component for olefin polymerization, production of olefin-based polymer and aminophenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new metal compound having high olefin polymerization activity, useful as a catalytic component for olefin polymerization, etc., comprising a nonmetallocene-based transition metal compound capable of being readily synthesized from a specific new aminophenol compound. SOLUTION: This new transition metal compound is shown by formula I [M is a transition metal atom of the group 4 of the periodic table; X and Y are each H, a halogen, a (substituted) 1-24C alkyl, a (substituted) 6-24C aryl, a (substituted) alkoxy or the like or X and Y may be arbitrarily bonded to form a ring; R is H, a (substituted) 1-24C alkyl, a (substituted) 6-24C aryl, a (substituted) 1-24C silyl or the like; Q is a 1-24C covalent bond cross linking group] and is useful as a catalytic component for olefin polymerization. The compound is obtained by reacting an aminophenol compound of formula II [R<1> to R<6> are each H, a (substituted) 1-24C alkyl, a (substituted) 6-24C aryl, etc.; R<7> is as shown for R<7> ; T is C, Se or Ge] with a transition metal compound of formula IV (Z<1> to Z<4> are each as shown for X).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound, a catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing an olefin polymer, and an aminophenol compound. More specifically, the present invention relates to a non-metallocene transition metal compound useful as an olefin polymerization catalyst component having high polymerization activity in olefin polymerization, an olefin polymerization catalyst component comprising the same, and an olefin polymerization catalyst using the same. And a method for efficiently producing an olefin homopolymer or copolymer in the presence of the olefin polymerization catalyst, and an aminophenol compound useful as a raw material for the transition metal compound.

[0002]

2. Description of the Related Art A catalyst comprising a transition metal compound of Group 4 of the Periodic Table having a group having two cyclopentadiene-type anion skeletons, a so-called metallocene, and methylaluminoxane or a specific boron compound. However, it has been reported in recent years that it exhibits high activity in olefin polymerization and has extremely useful characteristics industrially, such as producing an olefin polymer having a narrow molecular weight distribution and composition distribution (for example, , Tokiohei 1-502
No. 036, Japanese Translation of PCT International Publication No. 6-157651). Metallocene, by designing various ligands possessed by metallocene, in addition to being able to improve the activity in olefin polymerization, to improve the molecular weight, etc., by crosslinking the two ligands, Such as improvement in activity and stereoregular polymerization in the polymerization of α-olefins,
It is known that the design of the ligand contributes to the improvement of the catalyst performance (for example, JP-A-6-110314, JP-A-61-264010, JP-A-1-30170).
No. 4, JP-A-2-414303).

Further, a transition metal compound belonging to Group 4 of the periodic table having a group having one substituted cyclopentadiene-type anion skeleton and having a ligand in which a nitrogen atom is crosslinked with a silicon group, so-called geometric constraint It is also known that a polymerization catalyst comprising a complex and methylaluminoxane or a specific boron compound gives a polymer having high activity and high molecular weight in olefin polymerization (Japanese Patent Application Laid-Open No. 3-163088, JP-A-3-188092). However, for these transition metal compounds, particularly those having a cross-linked structure, it is difficult to synthesize the ligand and requires a plurality of steps. It was difficult.

On the other hand, a transition metal compound belonging to Group 4 of the periodic table having no group having a cyclopentadiene-type anion skeleton (so-called nonmetallocene), alkyl aluminum,
It has also been reported that the use of a polymerization catalyst comprising methylaluminoxane or a specific boron compound also exerts activity in olefin polymerization.
For example, JP-A-2-77412, JP-T-Hei-6-51
No. 0801, JP-A-8-176224, JP-A-8-176217, Journalof Ch
chemical Society, Chemical C
Ommunication 1996, p. 1375, describes an olefin polymerization catalyst using a non-crosslinked transition metal compound having a titanium-amide bond.

Also, US Pat. No. 5,318,935, JP-A-8-245713, Macromole
cures, Vol. 29, page 5241 (1996), O
rganometallics, vol. 15, p. 5085 (1996), Journal of Chemical
al Society, Chemical Commu
Nation, 1996, 2623 pages, Jou
rnal of Organometallic Che
mystery Vol. 506, p. 343 (1996)
Year), Organometallics Vol. 15 26
On page 72, an olefin polymerization catalyst comprising a crosslinked titanium-amide compound is described. However, olefin polymerization using these catalysts has not always been satisfactory in terms of polymerization activity.

Also, Organometallics, Vol. 16, p. 3282, p. 3303, describes a catalyst for olefin polymerization using a nitrogen-oxygen atom bridged transition metal compound in which a nitrogen atom is coordinated with a transition metal atom. Are listed. However, olefin polymerization using these catalysts has not always been satisfactory in terms of polymerization activity.

[0007]

SUMMARY OF THE INVENTION Under the above circumstances, an object of the present invention is to provide a non-metallocene transition metal which can be easily produced and isolated, and which can exhibit high polymerization activity in olefin polymerization. Compound, catalyst component for olefin polymerization comprising the same, highly active olefin polymerization catalyst containing the same, method for efficiently producing olefin homopolymer or copolymer in the presence of the catalyst, and the transition metal An object of the present invention is to provide a compound useful as a raw material of the compound.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention. That is, the present invention relates to a transition metal compound represented by the following general formula (1), a catalyst component for olefin polymerization comprising the same, the transition metal compound (A) and the following compound (B) and / or the following compound (C): And a method for producing an olefin polymer using the olefin polymerization catalyst, and an aminophenol compound represented by the following general formula (3). (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted sulfonyloxy group having 1 to 24 carbon atoms, an optionally substituted disubstituted amino group having 2 to 24 carbon atoms,
Or a silyl group having 1 to 24 carbon atoms which may be substituted. X and Y may be arbitrarily combined to form a ring. R is a hydrogen atom, an optionally substituted carbon number 1 to
An alkyl group of 24, optionally having 6 to 2 carbon atoms
An aryl group having 4 to 7 carbon atoms which may be substituted
An aralkyl group or an optionally substituted carbon number 1
To 24 silyl groups. Q represents a covalent bridging group having 1 to 24 carbon atoms. (B) an organoaluminum compound and / or an organoaluminum oxy compound (C) any one of the following compounds (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ( C2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) Boron represented by general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Compound (wherein B is a boron atom in a trivalent valence state,
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a silyl group containing 1 to 20 carbon atoms, 2
Disubstituted amino groups containing zero carbon atoms, which may be the same or different. G ⁺ is an inorganic or organic cation. L is a neutral Lewis base,
(LH) ⁺ is a Bronsted acid. ) (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, O represents an oxygen atom, and H represents a hydrogen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted C1-C24 sulfonyloxy group, an optionally substituted C2-C2
Represents a 24-disubstituted amino group or a silyl group having 1 to 24 carbon atoms which may be substituted; X and Y may be arbitrarily combined to form a ring. R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted, an aryl group having 6 to 24 carbon atoms which may be substituted, An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and an aryloxy group having 7 to 24 carbon atoms which may be substituted; Represents an aralkyloxy group, a disubstituted amino group having 2 to 24 carbon atoms which may be substituted, or a silyl group having 1 to 24 carbon atoms which may be substituted;
Further, they may be arbitrarily combined to form a ring. R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an aryl group optionally having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms which may be substituted Or an optionally substituted silyl group having 1 to 24 carbon atoms. T represents a carbon atom, a silicon atom or a germanium atom. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) Transition metal compound (A) The transition metal compound used as a catalyst component for olefin polymerization in the present invention is represented by the following general formula (1). (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted sulfonyloxy group having 1 to 24 carbon atoms, an optionally substituted disubstituted amino group having 2 to 24 carbon atoms,
Or a silyl group having 1 to 24 carbon atoms which may be substituted. X and Y may be arbitrarily combined to form a ring. R is a hydrogen atom, an optionally substituted carbon number 1 to
An alkyl group of 24, optionally having 6 to 2 carbon atoms
An aryl group having 4 to 7 carbon atoms which may be substituted
An aralkyl group or an optionally substituted carbon number 1
To 24 silyl groups. Q represents a covalent bridging group having 1 to 24 carbon atoms. )

In the general formula (1), M represents a transition metal atom belonging to Group 4 of the Periodic Table of the Elements (IUPAC Revised Edition of Inorganic Chemical Nomenclature 1989), preferably a titanium atom,
It is a zirconium atom or a hafnium atom, more preferably a titanium atom.

In the general formula (1), X and Y
Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted, an aryl group having 6 to 24 carbon atoms which may be substituted, and a carbon atom which may be substituted Aralkyl group having 1 to 24 carbon atoms, alkoxy group having 1 to 24 carbon atoms which may be substituted, aryloxy group having 6 to 24 carbon atoms which may be substituted, aralkyl having 7 to 24 carbon atoms which may be substituted An oxy group, an optionally substituted sulfonyloxy group having 1 to 24 carbon atoms,
It represents a disubstituted amino group having 2 to 24 carbon atoms which may be substituted, or a silyl group having 1 to 24 carbon atoms which may be substituted. X and Y may be arbitrarily combined to form a ring.

Specific examples of such a halogen atom include a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.

Examples of the alkyl group having 1 to 24 carbon atoms in X and Y in the general formulas (1) and (2) include methyl, ethyl, n-propyl, iso-propyl, and n-alkyl. -Butyl group, sec-butyl group, tert
-Butyl group, n-pentyl group, neo-pentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl, n-dodecyl group, n-pentadecyl group, n-eicosyl group, and the like. Preferred are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an amyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, and an aryloxy group such as a phenoxy group.

1 to 1 carbon atoms substituted with a halogen atom
Examples of the alkyl group of 20 include a fluoromethyl group,
Difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group,
Iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, penta Chloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group , Perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group,
Perchloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group,
Examples include a perbromohexyl group, a perbromooctyl group, a perbromododecyl group, a perbromopentadecyl group, and a perbromoeicosyl group.

The aryl group having 6 to 24 carbon atoms includes phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl,
2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group,
2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl Group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neo-pentylphenyl group, n-hexylphenyl group, Examples thereof include a naphthyl group and an anthracenyl group, and a phenyl group is preferable. Any of these aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, and an aryloxy group such as a phenoxy group.

Further, the above-mentioned X and Y having 7 to 7 carbon atoms.
Examples of the aralkyl group of 24 include a benzyl group and (2
-Methylphenyl) methyl group, (3-methylphenyl)
Methyl group, (4-methylphenyl) methyl group, (2,3
-Dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3
4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (pentamethylphenyl) methyl group,
(Ethylphenyl) methyl group, (n-propylphenyl) methyl group, (iso-propylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl)
Methyl group, (n-pentylphenyl) methyl group, (ne
o-pentylphenyl) methyl group, naphthylmethyl group,
Examples include an anthracenylmethyl group, and a benzyl group is preferable. Any of these aralkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, and an aryloxy group such as a phenoxy group.

In general formula (1), X and Y have 1 to 1 carbon atoms.
As the alkoxy group of 24, specifically, a methoxy group,
Ethoxy, n-propoxy, isopropoxy, n
-Butoxy group, sec-butoxy group, t-butoxy group,
n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadeoxy group, n-icosoxy group, and the like, preferably methoxy group, ethoxy group, and t-butoxy group. is there.
Any of these alkoxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The aryloxy group having 6 to 24 carbon atoms includes, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4 -Dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6
-Dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy , 2,4
5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group,
2,3,4,5-tetramethylphenoxy group, 2,3
4,6-tetramethylphenoxy group, 2,3,5,6-
Tetramethylphenoxy, pentamethylphenoxy, or ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n An aryloxy group having 6 to 20 carbon atoms such as -octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group. Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The above-mentioned X and Y have 7 to 7 carbon atoms.
Examples of the aralkyloxy group 24 include a benzyloxy group, a (2-methylphenyl) methoxy group, and (3
-Methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group,
(2,5-dimethylphenyl) methoxy group, (2,6-
(Dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) A) methoxy group, a (2,3,6-trimethylphenyl) methoxy group,
(2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n -Propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include an (octylphenyl) methoxy group, a (n-decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and a benzyloxy group is preferable.
Each of these aralkyloxyl groups is a fluorine atom,
It may be substituted with a halogen atom such as a chlorine atom, a bromine atom and an iodine atom.

The sulfonyloxy group represented by X and Y in the general formula (1) of the present invention is a compound represented by the general formula R ⁸ SO ₃ —, and may be a sulfonyloxy group having 1 to 24 carbon atoms which may be substituted. Is shown. Specifically, methanesulfonyl group, ethanesulfonyl group, dodecylsulfonyl group and the like
Examples include those in which ⁸ is an alkyl group, those in which a part thereof is substituted with halogen such as a trifluoromethanesulfonyl group, and those in which R ⁸ is an aryl group such as a p-toluenesulfonyl group.

The disubstituted amino group in X and Y in the general formula (1) of the present invention is an amino group having 2 to 24 carbon atoms substituted by two hydrocarbon groups, wherein the hydrocarbon group is For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, ter
1 to 10 carbon atoms such as t-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group
And an aryl group such as a phenyl group. Examples of such a disubstituted amino group having 2 to 24 carbon atoms include a dimethylamino group, a diethylamino group,
Di-n-propylamino group, diisopropylamino group,
Di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-
n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group and the like, preferably dimethylamino group or It is a diethylamino group.

The optionally substituted silyl group having 1 to 24 carbon atoms in X and Y in the general formula (1) of the present invention is a silyl group substituted with a hydrocarbon group, wherein the hydrocarbon group is Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, etc. Examples thereof include an alkyl group having 1 to 10 carbon atoms and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group.
Substituted silyl group, dimethylsilyl group, diethylsilyl group,
A disubstituted silyl group having 2 to 20 carbon atoms such as a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group,
Tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri- Examples thereof include a 3-substituted silyl group having 3 to 20 carbon atoms such as an n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group. In any of these silyl groups, the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

X in the general formulas (1) and (2)
And Y are preferably a halogen atom, an alkyl group, or an aralkyl group, and more preferably a chlorine atom, a methyl group, or a benzyl group.

In the general formula (1), R represents a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, Represents an aralkyl group having 7 to 24 carbon atoms, or a silyl group having 1 to 24 carbon atoms which may be substituted. The alkyl group, aryl group, aralkyl group, and silyl group as R are the same as those in X or Y described above.

Preferred alkyl groups as R include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, n-pentyl group, neo-pentyl group, amyl group, n-hexyl group, neo-hexyl group, n-octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group Or a norbornyl group.

The preferred aryl group as R is a phenyl group or a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group at the 2- and / or 6-position of the nitrogen atom on the aromatic ring. Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neo-pentyl group, amyl group, n-hexyl group, neo-hexyl group, n-octyl group, cyclopropyl group, cyclopentyl group And an aryl group having an alkyl group such as a cyclohexyl group and a cyclooctyl group.

Preferred aralkyl groups for R include a benzyl group, a naphthylmethyl group, an anthracenylmethyl group, a trityl group, and one or more methyl, ethyl or n-propyl group in the phenyl group of the benzyl group. Group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neo
-Having a pentyl group.

In the general formula (1), Q represents 1 carbon atom.
~ 24 covalent bridging groups. Such covalent bridging groups include, in addition to carbon atoms, atoms of group 14 of the periodic table such as silicon and germanium, atoms of group 15 such as nitrogen and phosphorus, and oxygen and nitrogen. It may contain a Group 16 atom. The covalent bridging group is preferably a covalent bridging group having 1 to 5 atoms in the main chain connecting adjacent oxygen atoms (O) and nitrogen atoms (N), and more preferably in the main chain. A covalent bridging group having 3 to 5 atoms. Q is particularly preferably a divalent group represented by the following general formula.

That is, the transition metal compound represented by the general formula (1) of the present invention is preferably a transition metal compound represented by the following general formula (2). (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted sulfonyloxy group having 1 to 24 carbon atoms, an optionally substituted disubstituted amino group having 2 to 24 carbon atoms,
Or a silyl group having 1 to 24 carbon atoms which may be substituted. X and Y may be arbitrarily combined to form a ring. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted 6 to 24 carbon atoms. 24 aryl groups, optionally substituted aralkyl groups having 7 to 24 carbon atoms, optionally substituted alkoxy groups having 1 to 24 carbon atoms, optionally substituted aryloxy groups having 6 to 24 carbon atoms An optionally substituted aralkyloxy group having 7 to 24 carbon atoms, an optionally substituted aralkyloxy group having 2 to 2 carbon atoms
Represents a 4-disubstituted amino group or a silyl group having 1 to 24 carbon atoms which may be substituted, and may be arbitrarily combined to form a ring. R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an aryl group optionally having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms which may be substituted Or an optionally substituted silyl group having 1 to 24 carbon atoms. T represents a carbon atom, a silicon atom or a germanium atom. )

In the general formula (2), M, X, Y,
N and O are the same as those in the general formula (1).

In the general formula (2), R ¹ , R ² , R
³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, An optionally substituted aralkyl group having 7 to 24 carbon atoms, an optionally substituted alkoxy group having 1 to 24 carbon atoms, an aryloxy group optionally having 6 to 24 carbon atoms, and optionally substituted An aralkyloxy group having 7 to 24 carbon atoms,
Represents a disubstituted amino group having 2 to 24 carbon atoms which may be substituted, or a silyl group having 1 to 24 carbon atoms which may be substituted; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ ,
The alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group, disubstituted amino group, and silyl group in R ⁵ and R ⁶ are the same as those in X or Y in the above general formula, respectively. .

In the general formula (2), R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently preferably an alkyl group, an aryl group, an aralkyl group or a silyl group, particularly preferably an alkyl group or a silyl group.

R ⁷ in the general formula (2) is the same as R in the general formula (1).

T in the general formula (2) represents a carbon atom, a silicon atom or a germanium atom, and is preferably a carbon atom or a silicon atom.

The transition metal compound represented by the general formula (1) is, for example, an amino alcohol compound (including an aminophenol or the like) based on the Q group of the general formula (1) HO-Q-NRH (provided that the compound is the same). , Q, R, N, and O are the same as those in the general formula (1), and H represents a hydrogen atom.) With a transition metal compound represented by the following general formula (4). Can be manufactured.

MZ ¹ Z ² Z ³ Z ⁴ (4) (wherein M represents a transition metal atom belonging to Group 4 of the periodic table;
¹ , Z ² , Z ³ and Z ⁴ are each independently a halogen atom, an optionally substituted alkoxy group having 1 to 24 carbon atoms, an optionally substituted aryloxy group having 6 to 24 carbon atoms, An optionally substituted aralkyloxy group having 7 to 24 carbon atoms, a sulfonyloxy group, an optionally substituted disubstituted amino group having 2 to 24 carbon atoms, an optionally substituted alkyl having 1 to 24 carbon atoms And represents an optionally substituted aryl group having 6 to 24 carbon atoms or an optionally substituted aralkyl group having 7 to 24 carbon atoms. )

The above-mentioned amino alcohol compounds are generally used widely as pharmaceuticals, agricultural chemicals or other basic intermediates. Therefore, there are many synthetic examples, and in many cases, they can be synthesized or purchased according to known literature. . More specific examples of the transition metal compound represented by the general formula (4) include, for example, titanium halides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, tetrakis (dimethylamino) titanium, and dichlorobis (dimethyl). Titanium amides such as amino) titanium, trichloro (dimethylamino) titanium, and tetrakis (diethylamino) titanium; alkoxytitaniums such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium, and trichloroisopropoxytitanium;
And compounds in which titanium in each of the above compounds is changed to zirconium or hafnium.

Among them, the transition metal compound represented by the general formula (2) can be easily produced and isolated, and examples thereof include the following production methods (I) and (II). (I) A method of producing by reacting an aminophenol compound represented by the following general formula (3) with a transition metal compound represented by the above general formula (4). (II) An aminophenol compound represented by the following general formula (3) is reacted with an organic alkali metal compound, an alkali metal hydride or an organic magnesium compound (hereinafter, may be abbreviated as “metal compound”). A salt compound, and then reacting with a transition metal compound represented by the above general formula (4).

[0040] (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, O represents an oxygen atom, and H represents a hydrogen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted C1-C24 sulfonyloxy group, an optionally substituted C2-C2
Represents a 24-disubstituted amino group or a silyl group having 1 to 24 carbon atoms which may be substituted; X and Y may be arbitrarily combined to form a ring. R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted, an aryl group having 6 to 24 carbon atoms which may be substituted, An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and an aryloxy group having 7 to 24 carbon atoms which may be substituted; Represents an aralkyloxy group, a disubstituted amino group having 2 to 24 carbon atoms which may be substituted, or a silyl group having 1 to 24 carbon atoms which may be substituted;
Further, they may be arbitrarily combined to form a ring. R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an aryl group optionally having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms which may be substituted Or an optionally substituted silyl group having 1 to 24 carbon atoms. T represents a carbon atom, a silicon atom or a germanium atom. )

In the general formula (3), R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , T, N and O are the same as those in the general formula (2).

In the method (II), the salt compound may or may not be isolated. In the method (II), the aminophenol compound, the metal compound and the transition metal compound represented by the general formula (4) can be mixed and reacted together.

In the production method (I) or (II), the amount of the transition metal compound represented by the general formula (4) is usually 0.5 to the amount of the aminophenol compound represented by the general formula (3). The range is from 3 to 3 times, preferably from 0.7 to 1.5 times.

Specific examples of the organic alkali metal compound used in the production method (II) include, for example, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, Examples thereof include organic lithium compounds such as trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium, and organic alkali metal compounds such as compounds obtained by changing lithium of these compounds to sodium, potassium, rubidium, or cesium. Preferably, one carbon atom
An alkali metal compound having an alkyl group of 10 to 10 is preferable, and a compound of lithium, sodium or potassium having an alkyl group having 1 to 10 carbon atoms is more preferable. More preferably, it is an alkyl lithium compound having an alkyl group having 1 to 10 carbon atoms.

Examples of the alkali metal hydride include lithium, sodium, potassium, rubidium and cesium hydrides, and preferably sodium hydride or potassium hydride.

The organic magnesium compound is, for example, a dialkylmagnesium compound or an alkylmagnesium halide, specifically, dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, diisopropylmagnesium, n-butylethylmagnesium, methylmagnesium iodide. , Methyl magnesium chloride, isopropyl magnesium halide and the like. Preferably, it is an alkyl magnesium halide.

The metal compound is preferably an organic alkali metal compound or an alkali metal hydride,
Particularly preferred is alkyllithium.

The amount of the metal compound to be used in the production method (II) is usually in a range of 1 to 5 moles per mol of the aminophenol compound represented by the general formula (3).

These reactions are generally carried out in the presence of a solvent. Examples of the solvent used include benzene, toluene, aromatic hydrocarbon solvents such as xylene and mesitylene, pentane, hexane, heptane, and the like. Aliphatic hydrocarbon solvents such as octane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, amide solvents such as hexamethylphosphoric amide and dimethylformamide, acetonitrile, propionitrile, acetone and diethyl ketone , Polar solvents such as methyl isobutyl ketone and cyclohexanone, and aprotic solvents such as halogenated solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. These solvents are used alone or in combination of two or more, and the amount of the solvent is usually 1 to 200 ml / g, preferably 3 to 200 ml / g based on the weight of the aminophenol compound represented by the general formula (3).
５０50 ml / g.

The reaction (I) can be carried out in the presence of a tertiary amine compound or the like. Here, as the tertiary amine compound used as an additive, triethylamine, diisopropylethylamine,
N, N, N ', N'-tetramethylethylenediamine and the like are preferably used. The amount used is 1 to 10 moles or more, preferably 1.5 to 5 moles, and more preferably 1.8 to 4 moles relative to the compound represented by the general formula (3).

The reaction temperature of the production method (I) is usually -100 ° C.
Carried out in the range from to 200 ° C., preferably at −80 ° C.
To 150 ° C. More preferably -50 to 120
It is in the range of ° C. The reaction temperature of the production method (II) is usually -10.
The temperature is 0 ° C. or higher and the boiling point of the solvent or lower, but preferably ranges from −80 ° C. to 40 ° C. when an organic alkali metal is used, and preferably ranges from 10 ° C. to 100 ° C. when an organic magnesium compound is used.

From the reaction solution containing the transition metal compound represented by the general formula (2) by the above reaction, if there is a solid component by-produced by the reaction, it is separated by filtration or the like in the presence of a predetermined solvent. Further, after heating and concentrating the solvent, or in another solvent alone or in a mixed solvent, it is possible to isolate the complex crystal by allowing the solvent to stand in a cool and dark place. Further, industrially, it is possible to efficiently precipitate and extract a target complex with high purity by, for example, gradually cooling it with stirring without standing still.

The compound represented by the general formula (3) in the present invention can be obtained by, for example, dehydrating and condensing an aldehyde compound having a hydroxyl group at the 2-position (for example, salicylaldehyde) or a ketone compound with an amine compound in a solvent. And a corresponding imine compound, which can then be easily synthesized by reduction with a metal hydride.

As the solvent used in the dehydration condensation reaction,
For example, benzene, aromatic hydrocarbon solvents such as toluene, pentane, aliphatic hydrocarbon solvents such as hexane, diethyl ether, ether solvents such as tetrahydrofuran, hexamethylphosphoric amide, amide solvents such as dimethylformamide, Polar solvents such as acetonitrile, acetone, nitrobenzene, dichloromethane,
Halogenated hydrocarbon solvents such as chlorobenzene, alcoholic solvents such as methanol, ethanol and 2-propanol can be used.

With respect to the dehydration-condensation reaction, the following methods can be mentioned. (A) A method in which an amine compound and an aldehyde compound are stirred and dehydrated and condensed in the presence of various drying agents. (B) A method of performing a dehydration condensation reaction using an apparatus such as a Dean-Stark water separator.

Examples of the desiccant used in the production method (a) include desiccants such as anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate, anhydrous potassium carbonate, anhydrous calcium chloride, and molecular sieve.

Examples of the solvent used in the reduction reaction include aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as pentane and hexane, and ether solvents such as diethyl ether and tetrahydrofuran. Can be used.

Examples of the metal hydride used in the reduction reaction include lithium aluminum hydride, diisobutylaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, sodium borohydride, sodium borohydride cyanide, and hydrogenated hydride. Metal hydride reducing agents such as lithium triethylboron and borane-tetrahydrofuran complex are exemplified.

(2) Compound (B) The compound (B) used in the present invention is an organic aluminum compound (B1) and / or an organic aluminum oxy compound (B2). Here, the organoaluminum compound (B1) has at least one Al-C bond in the molecule. Specific examples of the organoaluminum compound (B1) include trimethylaluminum,
Triethyl aluminum, tri normal propyl aluminum, tri normal butyl aluminum, tri isobutyl aluminum, tri t-butyl aluminum, tri isopropyl aluminum, tripentyl aluminum, tri normal hexyl aluminum, tri (2-methyl pentyl) aluminum, tri normal octyl aluminum, Diethylaluminum hydride, diisobutylaluminum hydride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, dimethylaluminum chloride, diethylaluminum chloride, dinormal propylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride Chloride, di t-butyl aluminum chloride, diisopropyl aluminum chloride, dipentyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, t- butyl aluminum dichloride, isopropyl aluminum dichloride, pentyl aluminum dichloride, and the like. Of these organoaluminum compounds,
Trialkylaluminum is preferred, and triethylaluminum or triisobutylaluminum is more preferably used.

Organic aluminum oxy compound (B2)
Can be used a known compound (aluminoxane), for example, a compound obtained by reacting one kind of trialkylaluminum with water, a compound obtained by condensing two or more kinds of trialkylaluminum with water, etc. Is used. Specifically, methylaluminoxane, ethylaluminoxane, propylaluminoxane,
Examples thereof include butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like.
Particularly, methylaluminoxane, isobutylaluminoxane, or methylisobutylaluminoxane is preferably used.

(3) Compound (C) In the present invention, the compound (C) includes (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , and (C2)
A boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C3) a general formula (LH) ⁺ (BQ ¹ Q ²
Q ³ Q ^{4) -} one of boron compound represented by the used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, Q ^{1 to} Q ³ are halogen atoms, and 1 to 20 A hydrocarbon group containing carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, a substituted silyl group containing 1-20 carbon atoms, an alkoxy group containing 1-20 carbon atoms, or 2- Disubstituted amino groups containing 20 carbon atoms, which may be the same or different.
Preferred Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated hydrocarbon group containing 1 to 20 carbon atoms.

Specific examples of the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, Tris (2,3,4,5
-Tetrafluorophenyl) borane, tris (3,4,
5-trifluorophenyl) borane, tris (2,3,
Examples thereof include 4-trifluorophenyl) borane and phenylbis (pentafluorophenyl) borane, and most preferably tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ are as defined above. (C
Is the same as Q ¹ to Q ³ in 1). G ⁺ is an inorganic or organic cation.

General formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-so
Specific examples of the boron compound (C2) represented include inorganic compounds
G, the cation of⁺Contains the ferrocenium cation,
Alkyl-substituted ferrocenium cation, silver cation, etc.
Is an organic cation G ⁺Contains triphenylcar
Benium cation and the like can be mentioned. G⁺Preferred as
Or a carbenium cation. (BQ¹Q^TwoQ^Three
Q^Four)^-Contains tetrakis (pentafluorophenyl)
Borate, tetrakis (2,3,5,6-tetrafluo
Rophenyl) borate, tetrakis (2,3,4,5-
Tetrafluorophenyl) borate, tetrakis (3
4,5-trifluorophenyl) borate, tetrakis
(2,2,4-trifluorophenyl) borate,
Nilbis (pentafluorophenyl) borate, tetra
Kis (3,5-bistrifluoromethylphenyl) bore
And the like.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-
Bis (trifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.

Formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), B is a boron in the trivalent valence state, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1) . L is a neutral Lewis base and (LH) ⁺ is a Bronsted acid.

The general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In Examples of the boron compound (C3) represented a Bronsted acid (the L-H) ⁺ is a trialkyl-substituted ammonium, N, N-dialkyl anilinium, dialkyl ammonium, triaryl And (BQ ¹ Q ² Q ³ Q ⁴ ) ^—
The same thing as the above is mentioned.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, di-iso-propylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) Examples thereof include borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (n-butyl) ammonium tetrakis ( Pentafluorophenyl) borate, or
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

The olefin polymerization catalyst of the present invention includes
An olefin polymerization catalyst comprising the transition metal compound (A) represented by the general formula (1) and the above (B) and / or the above (C) is used. When an olefin polymerization catalyst comprising two components (A) and (B) is used, the above-mentioned cyclic aluminoxane (B2) and / or linear aluminoxane (B3) are preferred as (B). As another preferred embodiment of the olefin polymerization catalyst, an olefin polymerization catalyst using the above (A), (B) and (C) is exemplified. ) Easy to use.

The amount of compound (B) to be used can be generally selected in a wide range such as 1 to 10000 moles as moles of aluminum atoms per mole of transition metal atoms in transition metal compound (A). Preferably, it is in the range of 1 to 3000 mol per mol of the transition metal atom.

The amount of compound (C) to be used can be generally selected from a wide range, for example, from 0.01 to 1000 mol per mol of transition metal atom in transition metal compound (A). Preferably, 0.1 mole per mole of transition metal atom
５０50 mol. More preferably, 0.1 to
20 moles.

As a method of supplying each of the catalyst components to the polymerization tank, for example, the catalyst components are supplied in an inert gas such as nitrogen or argon without any water in the presence of a monomer. The transition metal compound (A), the compound (B), and the compound (C) may be supplied individually or may be supplied in contact with each other in advance.

The polymerization can be carried out usually at a temperature ranging from -30 to 300 ° C., preferably from 0 to 28 ° C.
0 ° C, more preferably 20 to 250 ° C.

The polymerization pressure is not particularly limited, but is preferably from normal pressure to about 150 atm from the viewpoint of industrial and economical use. The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can range from 5 minutes to 40 hours.

The polymerization process may be either a continuous type or a batch type. Slurry polymerization with an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, and octane, solvent polymerization, liquid phase polymerization without solvent, or gas phase polymerization can also be performed.

In the present invention, as the monomer used for the polymerization, any of olefins and diolefins having 2 to 20 carbon atoms can be used, and two or more kinds of monomers can be used at the same time. Specific examples of these include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexene and the like are exemplified, but the present invention should not be limited to the above compounds. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and propylene and 1-butene. However, the present invention is limited to the above compounds. It should not be.

Further, in order to adjust the molecular weight of the olefin polymer of the present invention, a chain transfer agent such as hydrogen may be added.

[0079]

The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the examples. In addition, the measurement value of each item in an Example was measured by the following method.

(1) Intrinsic viscosity ([η]: dl / g) The intrinsic viscosity was measured at 135 ° C. in tetralin using an Ubbelohde viscometer.

(2) Weight average molecular weight (Mw) Measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was prepared using standard polystyrene. Model Millipore Waters 150CV type Column Shodex M / S 80 Measurement temperature 145 ° C, Solvent orthodichlorobenzene, Sample concentration 5mg / 8ml

(3) Determination of 1-hexene content of copolymer of ethylene and 1-hexene The 1-hexene content in the obtained polymer was determined from an infrared absorption spectrum. The measurement and calculation are described in the literature (Characterization of polyethylene by infrared absorption spectrum, written by Takayama, Usami et al., Or McRae,
M. A. , Madams, W .; F. , Die Makr
omoleculere Chemie, 177, 46
1 (1976)) using characteristic absorption derived from 1-hexene, for example, 1378 cm ^-1 . The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation). The 1-hexene content is determined by the degree of short-chain branching ((SCB) 10
(The number of short chain branches per 00 carbons).

(4) Measurement of Melting Point (Tm ° C.) Using a DSC-VII manufactured by Perkin-Elmer, it was measured under the following conditions. Temperature rise: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 40 ° C (5 ° C / min), hold for 10 minutes Measurement: 40 ° C to 160 ° C (5 ° C / min)

[0084] (5) ¹ The H-NMR measurement ¹ H-NMR measurement of, JEOL JNM-EX270
Was used. The measurement was performed at room temperature using the deuterated solvent described in the examples.

(6) The compounds (B) and (C) used at the time of polymerization in the following examples are as follows. Triisobutylaluminum: A commercial product manufactured by Tosoh Akzo Co., Ltd. was used. Aluminoxane (PMAO): PMAO-S manufactured by Tosoh Akzo Co., Ltd., toluene solution of (poly) methylaluminoxane (PMAO) Aluminoxane (MMAO): Heptane solution of (poly) methylisobutylaluminoxane manufactured by Tosoh Akzo, Inc. did. Triphenylcarbenium tetrakis (pentafluorophenyl) borate: commercially available from Tosoh Akzo Co., Ltd.
Triphenylcarbenium tetrakis (pentafluorophenyl) borate was used.

Embodiment 1 1-1. N- (2-hydroxybenzylidene) -ter
Synthesis of t-butylamine A solution of 25.23 g of salicylaldehyde in 50 ml of methylene chloride was placed in a 100 ml (one-necked) eggplant-shaped flask and cooled to 0 ° C. To this
100 ml of rt-butylamine was gradually added dropwise. After adding about 20 g of anhydrous magnesium sulfate, the mixture was stirred at room temperature for 18 hours. After completion of the reaction, solids derived from anhydrous magnesium sulfate are removed by filtration, and the filtrate is concentrated under reduced pressure to obtain N- (2-hydroxybenzylidene).
-Tert-Butylamine (yellow oil) was obtained almost quantitatively. ¹ H-NMR (CDCl ₃ ): 14.33 ppm (br
s, 1H, O H), 8.32 (s, 1H, C H = N),
7.23-7.31 (m, 2H, Ar), 6.93
(D, J = 8.3 Hz, 1H, Ar) 6.84 (dt,
J = 7.3, 1.3 Hz, 1H, Ar), 1.33
(S, 9H, (C H 3) 3 C)

1-2. Synthesis of N-tert-butyl-2-hydroxybenzylamine In a 1 L (four-neck) flask purged with argon, 9.52 g of lithium aluminum hydride and 10 parts of tetrahydrofuran were added.
0 ml was added and cooled to 0 ° C. In addition, N- (2-
(Hydroxybenzylidene) -tert-butylamine 2
A solution of 2.06 g of tetrahydrofuran in 100 ml was gradually added dropwise. After completion of the dropwise addition, the mixture was heated to room temperature, and then stirred for 4 hours. Then, the reaction was terminated by cooling to 0 ° C. and gradually dropping 40 ml of water. The produced white gel-like solid was removed by filtration, and about 5 g of anhydrous sodium sulfate was added to the filtrate, followed by drying by stirring. Solids derived from anhydrous sodium sulfate were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain N-tert-butyl-2.
-Hydroxybenzylamine 10.23 g (yield 46
%) As a white solid. ¹ H-NMR (CDCl ₃ ): 13 ppm (dt, J =
7.9, 1.3 Hz, 1H, Ar), 6.96 (d, J
= 7.6, 1H, Ar), 6.71-6.81 (m, 2
H, Ar), 3.92 (s , 2H, C H 2 N), 1.2
0 (s, 9H, (C H 3) 3 C)

1-3. Synthesis of N-tert-butyl-2-hydroxybenzylamine dilithium salt N was placed in a 200 ml (4-neck) flask purged with argon.
9.96 g of -tert-butyl-2-hydroxybenzylamine and 40 ml of diethyl ether were added, and -78 was added.
After cooling to 0 ° C., 70.3 ml of n-butyllithium (1.58M hexane solution) was gradually added dropwise. After the completion of the dropwise addition, the temperature was gradually raised to room temperature, and then the mixture was further stirred for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure, and hexane 40 m
After cooling to −78 ° C., the precipitated solid was separated by filtration through a glass filter, and dried under reduced pressure to give N-tert-butyl-2-hydroxybenzylamine dilithium salt in pale yellow. Obtained as a white solid.

1-4. [N (tBu) CH ₂ C ₆ H ₄ O]
Synthesis of TiCl ₂ (Complex A) A 100 ml (one-necked) flask purged with nitrogen was charged with a solution of 2.99 g of titanium tetrachloride in 50 ml of toluene, and then charged at −30.
Cooled to ° C. 2. N-tert-butyl-2-hydroxybenzylamine dilithium salt separately prepared
05 g little by little, and gradually warmed to room temperature.
Stirring was continued for 4 hours. After adding methylene chloride, the solid matter in the reaction solution was removed by filtration and washed with 50 ml of toluene × 3 times. The filtrate was concentrated under reduced pressure to about 10 ml,
By cooling to 8 ° C., 400.0 mg of (complex A)
(9% yield). ¹ H-NMR (CDCl ₃ ): 7.37 ppm (d, J
= 7.6 Hz, 1H, Ar), 7.30 (dt, J =
7.6, 1.6 Hz, 1H, Ar), 7.10 (dt,
J = 7.3, 1.0 Hz, 1H, Ar), 6.85 (d
d, J = 8.2, 1.0 Hz, 1H, Ar), 4.80
_{(S, 2H, C H 2} N), 1.66 (s, 9H, (C
H ₃ ) ₃ C)

Embodiment 2 2-1. Synthesis of N- (2-hydroxybenzylidene) -1-adamantylamine A 100 ml (one-neck) eggplant-shaped flask was charged with a solution of 9.76 g of adamantylamine in 50 ml of methylene chloride,
Cooled to 0 ° C. 7.90 g of salicylaldehyde
Was gradually added dropwise. After about 5 g of anhydrous magnesium sulfate was added thereto, the mixture was stirred at room temperature for 17 hours. After completion of the reaction, solids derived from anhydrous magnesium sulfate were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain N- (2
-Hydroxybenzylidene) -1-adamantylamine (yellow solid) was obtained almost quantitatively. ¹ H-NMR (CDCl ₃ ): 14.45 (brs, 1
H, O H), 8.31 ( s, 1H, C H = N), 7.2
2-7.31 (m, 2H, Ar), 6.92 (dd, J
= 8.2, 0.6 Hz, 1H, Ar), 6.82 (d
t, J = 7.6, 1.0 Hz, 1H, Ar), 2.18
(M, 3H), 1.84-1.85 (m, 6H), 1.
67-1.79 (m, 6H)

2-2. N- (1-adamantyl) -2-
Synthesis of hydroxybenzylamine 5.28 g of lithium aluminum hydride and 50 ml of tetrahydrofuran were placed in a 300 ml (four-neck) flask purged with argon, and cooled to 0 ° C. In addition, N- (2
A solution of 19.80 g of (-hydroxybenzylidene) -1-adamantylamine in 100 ml of tetrahydrofuran was gradually added dropwise. After completion of the dropwise addition, the mixture was heated to room temperature, and then stirred for 22 hours. Then, cool to 0 ° C and add
The reaction was terminated by gradually adding 0 ml dropwise.
The obtained gel was separated by filtration, and vigorously stirred and extracted in 200 ml of tetrahydrofuran + 200 ml of water. The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was recrystallized with a mixed solvent of toluene, ethanol and water to obtain 6.90 g (yield 34%) of N- (1-adamantyl) -2-hydroxybenzylamine as a gray powder.

2-3. N- (1-adamantyl) -2-
Synthesis of hydroxybenzylamine dilithium salt In a 200 ml (4-neck) flask purged with argon, N-
A solution of 6.88 g of (1-adamantyl) -2-hydroxybenzylamine in 50 ml of diethyl ether was added thereto.
Cooled to 78 ° C. To this, n-butyl lithium (1.5
(4M, hexane solution) 34.7 ml was gradually added dropwise.
After completion of the dropping, the temperature was gradually raised to room temperature, and then stirring was performed for 4 hours. Thereafter, the solvent was distilled off under reduced pressure, 40 ml of hexane was added, and the mixture was cooled to -78 ° C. -Adamantyl) -2-
7.19 g of hydroxybenzylamine dilithium salt
(99% yield) as a white solid.

2-4. [N (C ₁₀ H ₁₅ ) CH ₂ C ₆ H
Synthesis of ₄ O] TiCl ₂ (Complex B) To a 100 ml (one-necked) flask purged with nitrogen, 1.15 g of titanium tetrachloride and 50 ml of toluene were added, and the mixture was added at -30 ° C.
And cooled. To this, 1.60 g of separately prepared N- (1-adamantyl) -2-hydroxybenzylamine dilithium salt was added, and after gradually warming to room temperature, stirring was continued for 48 hours. After addition of methylene chloride, solids in the reaction solution were removed by filtration, and this was further added to methylene chloride 5
Washing was performed with 0 ml × 3 times. The filtrate was concentrated to about 50 ml under reduced pressure, and cooled to -30 ° C to obtain (Complex B) as red-brown crystals. 0.63g in total up to the second crystal
(Yield 28%). ¹ H-NMR (CDCl ₃ ): 7.36 ppm (d, J =
7.3, 1H, Ar), 7.29 (dt, J = 7.6,
1.3 Hz, Ar), 7.09 (dt, J = 7.6,
1.3 Hz, Ar), 6.84 (d, J = 8.3 Hz,
1H, Ar), 4.83 (s , 2H, C H 2 N), 2.
28 (m, 3H), 2, 24 (m, 6H), 1.79
(M, 6H)

Example 3 3-1.2-tert-butyl-1-hydroxy-4-
Synthesis of methylbenzaldehyde 2-tert-
Butyl-4-methylphenol 199.36 g tolue
200 ml of solution was added thereto, and tin tetrachloride 49.65 was added thereto.
g of toluene in 100 ml was added dropwise at room temperature. Dripping
After completion, cool the flask to 0 ° C and add triethylamine 7
A solution of 6.89 g of toluene in 100 ml was gradually added dropwise.
Was. After completion of the dropwise addition, the mixture was further stirred at 0 ° C. for 40 minutes.
Then, the temperature was gradually raised to room temperature, and paraformaldehyde 8
1.57 g was added in small portions. Stir for 21 hours under reflux conditions
After cooling to room temperature, 4N hydrochloric acid was adjusted to pH <1.
Added until it was. 500 ml of diethyl ether x 3 times
The crude product is obtained by extracting and distilling off the solvent under reduced pressure.
Obtained. This is recrystallized with a mixed solvent of ethanol and heptane.
To give 2-tert-butyl-1-hydroxy-
4-methylbenzaldehyde as a second needle crystal
83.18 g (36% yield) was obtained including the crystals. ¹ H-NMR (CDCl_Three): 60 ppm (s, 1H),
9.83 (s, 1H), 7.33 (m, 1H, Ar),
717-7.18 (m, 1H, Ar), 2.32 (s,
3H, (CH_Three)), 1.41 (s, 9H, (CH_Three)_Three
C)

3-2. N- (2-tert-butyl-1
-Hydroxy-4-methylbenzylidene) -tert-
Synthesis of butylamine In a 100 ml (one-neck) eggplant-shaped flask, 2-tert
-Butyl-1-hydroxy-4-methylbenzaldehyde (15.32 g) in methylene chloride (30 ml) was added.
Cooled to ° C. 50 ml of tert-butylamine
Was gradually added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, about 5 g of anhydrous magnesium sulfate was added, and the mixture was stirred at room temperature for 47 hours. After completion of the reaction, solids derived from anhydrous magnesium sulfate were removed by filtration, and the filtrate was concentrated under reduced pressure to give N- (2-tert-butyl-1-hydroxy-
4-methylbenzylidene) -tert-butylamine 1
8.39 g (93% yield) was obtained as a yellow oil. ¹ H-NMR (CDCl ₃ ): 47 ppm (brs, 1
H, O H), 8.30 ( s, 1H, C H = N), 7.1
0 (d, J = 2.0 Hz, 1H, Ar), 6.91
(D, J = 1.6 Hz, 1H, Ar), 2.28 (s,
3H, (CH ₃ )), 1.43 (s, 9H, (CH ₃ ) ₃
C), 1.33 (s, 9H, (CH ₃ ) ₃ C)

3-3. N- (tert-butyl) -2-
Hydroxy-3-tert-butyl-5-methylbenzyl
Synthesis of Luamine Hydrogen in a 500 ml (four-neck) flask purged with argon
4.22 g of lithium aluminum chloride, tetrahydrofura
100 ml and cooled to 0 ° C. In addition, N-
(2-tert-butyl-1-hydroxy-4-methyl
13.49 g of benzylidene) -tert-butylamine
Of tetrahydrofuran in 100 ml
Was. After completion of the dropwise addition, the mixture was stirred for 4 hours under reflux. So
After that, cool to 0 ° C and gradually add about 15 ml of 4N hydrochloric acid.
To stop the reaction. Formed white gel-like solid
The form was removed by filtration, and about 5% of anhydrous sodium sulfate was added to the filtrate.
g was added and the mixture was stirred and dried. Sulfuric anhydride
Solids derived from sodium are removed by filtration, and the filtrate is depressurized.
N- (tert-butyl) -2-
Hydroxy-3-tert-butyl-5-methylbenzyl
12.13 g of ruamine (89% yield) as a white solid
Obtained.¹ H-NMR (CDCl_Three): 6.97 ppm (d, J =
2.0 Hz, 1 H, Ar), 6.70 (d, J = 1.6)
Hz, 1H, Ar), 3.87 (s, 2H, (CH
_TwoN)), 2.23 (s, 3H, (CH_Three)), 1.41
(S, 9H, (CH_Three)_ThreeC), 1.20 (s, 9H,
(CH_Three)_ThreeC)

3-4. N- (tert-butyl) -2-
Synthesis of hydroxy-3-tert-butyl-5-methylbenzylamine dilithium salt In a 100 ml (four-necked) flask purged with argon, N- was added.
(Tert-butyl) -2-hydroxy-3-tert
A solution of 5.52 g of -butyl-5-methylbenzylamine in 20 ml of diethyl ether was added, and the mixture was cooled to -78 ° C. To this, 28.7 ml of n-butyllithium (1.54M, hexane solution) was gradually added dropwise. After completion of the dropping, the temperature was gradually raised to room temperature, and then stirring was performed for 4 hours.
Thereafter, the solvent was distilled off under reduced pressure, 40 ml of hexane was added, and the mixture was cooled to -78 ° C. -Butyl) -2-hydroxy-3
5.33 g (92% yield) of -tert-butyl-5-methylbenzylamine dilithium salt was obtained as a white solid.

3-5. [N (tBu) CH ₂ (3-tB
Synthesis of u, 5-Me) C ₆ H ₄ O] TiCl ₂ (Complex C) 1.17 g of titanium tetrachloride in 30 ml of toluene was added to a nitrogen-substituted 100 ml (one-necked) flask, and -30 ° C.
And cooled. To this, 1.66 g of separately prepared N- (tert-butyl) -2-hydroxy-3-tert-butyl-5-methylbenzylamine dilithium salt was added,
After the temperature was gradually raised to room temperature, stirring was continued for 116 hours.
After adding methylene chloride, the solid substance in the reaction solution was removed by filtration and washed with 50 ml of methylene chloride × 3 times. The filtrate was concentrated to about 30 ml under reduced pressure, and cooled to -30 ° C to obtain (Complex C) as red needle crystals. 0.69 g (30% yield) in total up to the second crystal. 7.03-7.10 ppm (m, 2H, Ar), 4.7
4 (s, 2H, (C H 2N)), 2.34 (s, 3H,
(CH ₃ )), 1.64 (s, 9H, (CH ₃ ) ₃ C),
1.44 (s, 9H, (CH 3) 3 C)

Example 4 A 1-liter stirring-type stainless steel autoclave was purged with nitrogen, charged with 300 ml of purified toluene, and saturated with 4.0 kgf / cm ² of ethylene gas while heating to a polymerization temperature of 60 ° C. to prepare for polymerization. Did. On the other hand, a 100-ml flask equipped with a magnetic stirrer was purged with nitrogen, and 10 ml of purified toluene, 4.7 mmol of triisobutylaluminum, and 9.4 μmol of (complex B) synthesized in Example 2 were added under a nitrogen atmosphere. For 5 minutes. This catalyst solution was injected into an autoclave, and then a small amount of a toluene solution of triphenylcarbenium tetrakispentafluorophenylborate in an equimolar amount to the catalyst was injected, and polymerization was carried out at 60 ° C. for 60 minutes. During this time, ethylene gas was continuously fed at 4.0 kgf / cm ² . Thereafter, the polymerization was stopped by press-fitting 15 ml of ethanol. Unreacted ethylene gas was purged, and the content of the autoclave was poured into about 4-fold ethanol, and the precipitated polymer was separated by filtration and dried at 60 ° C. for about 4 hours. As a result, 9.9 g of polyethylene was obtained. The weight average molecular weight (M
w) was 455,000.

Example 5 The procedure of Example 4 was repeated, except that 10 ml of 1-hexene was added. As a result, 8.7 g of an ethylene / 1-hexene copolymer was obtained. The melting point (Tm) of the obtained copolymer was 113.5 ° C. The weight average molecular weight (Mw) of the obtained ethylene / 1-hexene copolymer was 384,000.

Example 6 A 1-liter stirred autoclave made of stainless steel was purged with nitrogen, charged with 300 ml of purified toluene, and saturated with 4.0 kgf / cm ² of ethylene gas while heating to a polymerization temperature of 60 ° C. to prepare for polymerization. Did. On the other hand, a 100 ml flask equipped with a magnetic stirrer was purged with nitrogen, and 10 ml of purified toluene and PMAO1 were placed under a nitrogen atmosphere.
0.7 mmol, then synthesized in Example 2 (Complex B)
Was added and stirred and mixed at room temperature for 5 minutes.
This catalyst solution was pressed into an autoclave and heated at 60 ° C. for 6 hours.
Polymerization was performed for 0 minutes. During this time, ethylene gas was 4.0 k
Feeding was continued at gf / cm ² . Thereafter, the polymerization was stopped by press-fitting 15 ml of ethanol. Unreacted ethylene gas is purged, and the contents of the autoclave are reduced to approx.
The mixture was poured into twice the amount of ethanol, and the precipitated polymer was separated by filtration and dried at 60 ° C. for about 4 hours. As a result, 2.4 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 494,000.

Example 7 In Example 6, 8.3 mmol of MMAO (hexane solution) and 8.3 μm of (complex B) were used in place of PMAO.
The same procedure as in Example 6 was carried out except that the polymerization was carried out in heptane using mol. As a result, 1.7 g of polyethylene was obtained.

Example 8 In Example 4, triisobutylaluminum was replaced with 1
Example 4 was carried out in the same manner as in Example 4, except that 2.5 mmol and (Complex A) synthesized in Example 1 were used in an amount of 25 μmol instead of (Complex B). As a result, 15.4 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 361,000.

Example 9 In Example 4, triisobutylaluminum was replaced with 3.
7 mmol, 7.4 g of (complex A) synthesized in Example 1 was used instead of (complex B), and 10 g of 1-butene was used.
In addition, polymerization temperature 70 ° C, ethylene pressure 6.0 kgf / cm
^The procedure was performed in the same manner as in Example 4 except that the polymerization was performed in Step ² .
As a result, 2.7 g of an ethylene / 1-butene copolymer was obtained.

Example 10 In Example 4, triisobutylaluminum was replaced with 3.
9 mmol, 7.8 μmol of (complex A) synthesized in Example 1 in place of (complex B), and 1-hexene was used in 10
The procedure was carried out in the same manner as in Example 4 except that the polymerization was carried out with the addition of 0.1 ml. As a result, 6.7 g of an ethylene / 1-hexene copolymer was obtained. The weight average molecular weight (Mw) of the obtained ethylene / 1-hexene copolymer was 363,000. The melting point (Tm) of the obtained copolymer was 119.6 ° C.

Example 11 In Example 6, 30.7 mmol of PMAO and (Complex A) synthesized in Example 1 were replaced with 30.7 mmol of (Complex B).
The same operation as in Example 6 was performed except that 0.7 μmol was used. As a result, 4.2 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 154.
0000.

Example 12 In Example 6, 40.5 mmol of MMAO (hexane solution) was used instead of PMAO, and 40.5 μmol of (complex A) synthesized in Example 1 was used instead of (complex B). The procedure was as in Example 6, except in heptane. As a result, 16.2 g of polyethylene was obtained.

Example 13 In Example 6, 18.9 mmol of MMAO (hexane solution) was used instead of PMAO, and 18.9 μmol of (Complex A) synthesized in Example 1 was used instead of (Complex B). The procedure was the same as in Example 6, except that 10 ml of hexene was added. As a result, 8.6 g of an ethylene / 1-hexene copolymer was obtained. The melting point (Tm) of the obtained copolymer was 123.1 ° C.

Example 14 In Example 4, triisobutylaluminum was replaced with 3.
Example 4 was carried out in the same manner as in Example 4 except that 6.3 μmol of (complex C) synthesized in Example 3 was used instead of 2 mmol (complex B). As a result, 1.6 g of polyethylene was obtained. The weight average molecular weight (M
w) was 487000.

Example 15 In Example 4, triisobutylaluminum was replaced with 2.
5 mmol, 4.9 μmol of (complex C) synthesized in Example 3 instead of (complex B), and 10 g of 1-butene
In addition, polymerization temperature 70 ° C, ethylene pressure 6.0 kgf / cm
^The procedure was performed in the same manner as in Example 4 except that the polymerization was performed in Step ² .
As a result, 1.7 g of an ethylene / 1-butene copolymer was obtained.

Example 16 In Example 4, triisobutylaluminum was replaced with 3.
6.3 μmol of (complex C) synthesized in Example 3 was used instead of 2 mmol and (complex B), and 1-hexene was used in 10
The procedure was performed in the same manner as in Example 4 except that ml was added. As a result, 1.4 g of an ethylene / 1-hexene copolymer was obtained. The weight average molecular weight (Mw) of the obtained ethylene / 1-hexene copolymer was 565,000.

Example 17 In Example 6, 6.0 mmol of PMAO and 6.0 of (complex C) synthesized in Example 3 were used instead of (complex B).
The procedure was performed in the same manner as in Example 6, except that μmol was used. As a result, 0.55 g of polyethylene was obtained.

Example 18 In Example 6, 6.6 mmol of PMAO and 6.6 of (Complex C) synthesized in Example 3 were used instead of (Complex B).
μmol, 10 g of 1-butene was added, and the polymerization temperature was 70
The procedure was carried out in the same manner as in Example 6, except that the polymerization was carried out at a temperature of 6.0 ° C. and an ethylene pressure of 6.0 kgf / cm ² . As a result, 0.66
g of ethylene / 1-butene copolymer was obtained.

Example 19 In Example 6, 9.8 mmol of MMAO (hexane solution) was used instead of PMAO, and 9.8 μmol of (Complex C) synthesized in Example 3 was used instead of (Complex B). Was carried out in the same manner as in Example 6 except that was carried out in heptane. As a result, 4.8 g of polyethylene was obtained.

Example 20 In Example 6, 8.7 mmol of MMAO (hexane solution) was used instead of PMAO, and 8.7 μmol of (Complex C) synthesized in Example 3 was used instead of (Complex B).
-The procedure was as in Example 6, except that 10 ml of hexene were added and the polymerization was carried out in heptane. As a result, 5.5 g
Of ethylene / 1-hexene copolymer was obtained.

[0116]

According to the present invention, there is provided a non-metallocene transition metal compound which can be easily synthesized and which can exhibit high polymerization activity in olefin polymerization. An olefin polymerization catalyst using the transition metal compound as an olefin polymerization catalyst component has high activity, and an olefin homopolymer or copolymer can be efficiently produced using this polymerization catalyst.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07F 7/00 C07F 7/00 A 7/28 7/28 F 7/30 7/30 D C08F 4/645 C08F 4/645 10 / 00 10/00 210/16 210/16

Claims (9)

[Claims] 1. A transition metal compound represented by the following general formula (1). (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted sulfonyloxy group having 1 to 24 carbon atoms, an optionally substituted disubstituted amino group having 2 to 24 carbon atoms,
Or a silyl group having 1 to 24 carbon atoms which may be substituted. X and Y may be arbitrarily combined to form a ring. R is a hydrogen atom, an optionally substituted carbon number 1 to
An alkyl group of 24, optionally having 6 to 2 carbon atoms
An aryl group having 4 to 7 carbon atoms which may be substituted
An aralkyl group or an optionally substituted carbon number 1
To 24 silyl groups. Q represents a covalent bridging group having 1 to 24 carbon atoms. ) 2. The transition metal compound according to claim 1, represented by the following general formula (2). (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted sulfonyloxy group having 1 to 24 carbon atoms, an optionally substituted disubstituted amino group having 2 to 24 carbon atoms,
Or a silyl group having 1 to 24 carbon atoms which may be substituted. X and Y may be arbitrarily combined to form a ring. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted 6 to 24 carbon atoms. 24 aryl groups, optionally substituted aralkyl groups having 7 to 24 carbon atoms, optionally substituted alkoxy groups having 1 to 24 carbon atoms, optionally substituted aryloxy groups having 6 to 24 carbon atoms An optionally substituted aralkyloxy group having 7 to 24 carbon atoms, an optionally substituted aralkyloxy group having 2 to 2 carbon atoms
Represents a 4-disubstituted amino group or a silyl group having 1 to 24 carbon atoms which may be substituted, and may be arbitrarily combined to form a ring. R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an aryl group optionally having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms which may be substituted Or an optionally substituted silyl group having 1 to 24 carbon atoms. T represents a carbon atom, a silicon atom or a germanium atom. ) 3. The transition metal compound according to claim 1, wherein M is a titanium atom or a zirconium atom. 4. The transition metal compound according to claim 2, wherein T is a carbon atom or a silicon atom. 5. A catalyst component for olefin polymerization, comprising the transition metal compound according to claim 1. 6. An olefin polymerization method comprising using the transition metal compound (A) according to any one of claims 1 to 4 and the following compound (B) and / or the following compound (C). catalyst. (B) an organoaluminum compound and / or an organoaluminum oxy compound (C) a boron compound of any of the following compounds (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2 ) Boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) Boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (Wherein, B is a boron atom in a trivalent valence state, Q ^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogen group containing 1 to 20 carbon atoms. hydrocarbon group, a silyl group containing from 1 to 20 carbon atoms, a disubstituted amino group containing 1-20 carbon atoms, they may be different even in the same. G ⁺ is an inorganic Or L is a neutral Lewis base; L-H) ⁺ is a Bronsted acid.) 7. A process for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to claim 6. 8. The olefin polymer according to claim 7, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.
The method for producing the olefin polymer according to the above. 9. An aminophenol compound represented by the following general formula (3). (Wherein, M represents a transition metal atom of Group 4 of the periodic table;
Represents a nitrogen atom, O represents an oxygen atom, and H represents a hydrogen atom. X and Y are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, and optionally substituted An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and 7 to 24 carbon atoms which may be substituted; 24 aralkyloxy groups, an optionally substituted C1-C24 sulfonyloxy group, an optionally substituted C2-C2
Represents a 24-disubstituted amino group or a silyl group having 1 to 24 carbon atoms which may be substituted; X and Y may be arbitrarily combined to form a ring. R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted, an aryl group having 6 to 24 carbon atoms which may be substituted, An aralkyl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms which may be substituted, an aryloxy group having 6 to 24 carbon atoms which may be substituted, and an aryloxy group having 7 to 24 carbon atoms which may be substituted; Represents an aralkyloxy group, a disubstituted amino group having 2 to 24 carbon atoms which may be substituted, or a silyl group having 1 to 24 carbon atoms which may be substituted;
Further, they may be arbitrarily combined to form a ring. R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 24 carbon atoms, an aryl group optionally having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms which may be substituted Or an optionally substituted silyl group having 1 to 24 carbon atoms. T represents a carbon atom, a silicon atom or a germanium atom. )