JP3202366B2 - Production method of .ALPHA.-olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an .alpha.-olefin polymer. More specifically, the present invention comprises a specific transition metal compound component (component (A)), a normal organoaluminum compound component (component (B)), and a specific organoaluminum compound component (component (C)). The present invention relates to a method for producing an α-olefin polymer using a catalyst.

[0002]

2. Description of the Related Art A method for producing a poly-α-olefin by combining an alumoxane and a transition metal compound is well known (JP-A-58-45205 and JP-A-58-19).
No. 309, No. 60-35007, No. 61-13031
No. 4, No. 62-230802, No. 63-142004
Nos. 63-23409, 64-51408 and 64-66214). However, these techniques are considered to have an industrial problem because the production cost is high because the activity per aluminum atom is low, and a large amount of aluminum remains in the olefin polymer.

[0003] Various proposals have been made for the purpose of solving these problems (JP-A-61-21307, JP-A-61-21307).
3-130601, 64-16803, JP-A-Hei 2
-22308 and 2-167307).
Although the activity per aluminum is somewhat improved by these proposals, such alumoxane has poor solubility, is difficult to handle and it is difficult to remove aluminum, so that the quality of the olefin polymer deteriorates and the hue deteriorates. It seems that further improvement is necessary.

As another proposal, there is a method of coexisting other organoaluminum compounds and the like in methylalumoxane (JP-A-60-260602 and JP-A-60-13060).
No. 4, 63-89506, 63-178108
Nos. 63-218707, 64-9206, JP-A-1-315407, 2-22306 and 2-167310. Although these proposals have reduced the amount of methylalumoxane used, the activity per aluminum is still insufficient, and further improvement is desired.

On the other hand, as a new attempt, an olefin polymerization catalyst component comprising an alumoxane compound having two or more types of alkyl groups has been proposed (JP-A-2-247).
No. 201, 2-250886 and 4-46906
Nos. 4,264,410 and 4-266910. Furthermore, there is a proposal to use an alumoxane compound in which a part of the alkyl group of the alumoxane compound has been converted to hydrogen (Japanese Patent Application Laid-Open No. 3-139503).
However, all of these alumoxane compounds have a high degree of association and must be used in many cases in order to maintain high activity, and they are only soluble in aromatic solvents. There are many.

On the other hand, as an attempt to reduce the molecular weight of a polymer,
It has been proposed to use a tetraalkylalumoxane compound (JP-A-3-197514). This alumoxane compound is advantageous in that it is easily dissolved in an aliphatic hydrocarbon solvent.However, although it exhibits activity in ethylene polymerization, the polymerization activity of α-olefins such as propylene seems to be extremely low. Further improvement is desired.

A reaction product of an organoaluminum compound and an oxygen-supplying compound other than water (for example, boroxine or alkyltin oxide) has been proposed (Japanese Patent Application Laid-Open No. 2-210).
256686, 4-304202, 4-304
No. 203 and 4-304206). But,
What is obtained by these methods is an alumoxane having an Al-O-Al bond, which seems to have the same problems as described above.

On the other hand, as an organoaluminum compound other than the alumoxane compound, a reaction product of a dihydric alcohol or a divalent amine with an organoaluminum compound has been proposed (JP-A-3-62806). However, when the organoaluminum compound obtained by this reaction is combined with a metallocene compound, usually only a very low polymerization activity can be obtained, so that it is insufficient as a substitute for the alumoxane compound, and further improvement is desired. [Summary of the Invention]

[0009]

The problem to be solved by the present invention is to solve the various problems found in the above prior art.

[0010]

[Means for Solving the Problems]

<Summary> The present invention has been made as a result of studies for solving the above problems.

That is, the method for producing an α-olefin polymer according to the present invention comprises contacting an α-olefin with a catalyst comprising the following components (A), (B) and (C) to polymerize the catalyst. It is a feature.

[0012] Component (A): general formula (1) or the transition metal compound represented by _{(2), Q a (C} 5 H 5-ab R 4 b) (C 5 H 5-ac R 5 c _{) MeXY (1) S a (} C 5 H 5-ad R 6 d) ZMeXY (2) ( _{where, (C 5 H 5-ab} R 4 b), (C 5 H 5-ac R 5
_c ) and (C ₅ H _5-ad R ⁶ _d ) are each a conjugated 5-membered ring ligand coordinated to Me (R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon residue having 1 to 20 carbon atoms; A halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group (R ⁴ ,
R ⁵ and R ⁶ may be the same or different, and a plurality of R ⁴ , R ⁵ and R ⁶ may be bonded to each other), and Q is a bridge between two conjugated five-membered ligands. A binding group selected from the group consisting of an alkylene group, a silylene group, and a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, where S is a conjugated five-membered ring ligand and a Z group An alkylene group, a silylene group, and germanium, phosphorus,
What is selected from the group consisting of hydrocarbon groups containing nitrogen, boron or aluminum, Z is oxygen, sulfur, an alkoxy group, a thioalkoxy group, a silicon-containing hydrocarbon group,
A nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, Me is titanium, zirconium and hafnium, and X and Y are each a hydrogen, halogen group, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing Hydrocarbon group (X and Y may be the same or different)
A represents 0 or 1, b represents an integer of 0 ≦ b ≦ 5, c represents an integer of 0 ≦ c ≦ 5, and d represents an integer of 0 ≦ d ≦ 5. ) Component (B): an organoaluminum compound, Component (C): a compound having the following structure.

[0013]

Embedded image (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ² is hydrogen, halogen, a siloxy group, a lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and each of the four R ² may be the same or different. Also, another method for producing an α-olefin polymer according to the present invention comprises contacting an α-olefin with a catalyst comprising the following components (A), (B) and (C) to polymerize the polymer: It is characterized by the following.

[0014] Component (A): general formula (1) or the transition metal compound represented by _{(2), Q a (C} 5 H 5-ab R 4 b) (C 5 H 5-ac R 5 c _{) MeXY (1) S a (} C 5 H 5-ad R 6 d) ZMeXY (2) ( _{where, (C 5 H 5-ab} R 4 b), (C 5 H 5-ac R 5
_c ) and (C ₅ H _5-ad R ⁶ _d ) are each a conjugated 5-membered ring ligand coordinated to Me (R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon residue having 1 to 20 carbon atoms; A halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group (R ⁴ ,
R ⁵ and R ⁶ may be the same or different, and a plurality of R ⁴ , R ⁵ and R ⁶ may be bonded to each other), and Q is a bridge between two conjugated five-membered ligands. A binding group selected from the group consisting of an alkylene group, a silylene group, and a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, where S is a conjugated five-membered ring ligand and a Z group An alkylene group, a silylene group, and germanium, phosphorus,
What is selected from the group consisting of hydrocarbon groups containing nitrogen, boron or aluminum, Z is oxygen, sulfur, an alkoxy group, a thioalkoxy group, a silicon-containing hydrocarbon group,
A nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, Me is titanium, zirconium and hafnium, and X and Y are each a hydrogen, halogen group, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing Hydrocarbon group (X and Y may be the same or different)
A represents 0 or 1, b represents an integer of 0 ≦ b ≦ 5, c represents an integer of 0 ≦ c ≦ 5, and d represents an integer of 0 ≦ d ≦ 5. ) Component (B): an organoaluminum compound, Component (C): a reaction product of the following components (i) and (ii).

Component (i):

[0016]

Embedded image (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms.) Component (ii): an organoaluminum compound. <Effect> According to the method for producing an α-olefin polymer according to the present invention,
In addition to greatly improving the catalytic activity per aluminum atom, expensive alumoxane compounds are not required, and there is no need to use an aromatic hydrocarbon solvent which is an industrial constraint. Although the reason for the effect of the present invention has not yet been elucidated, it is presumed that the active site formation by the component (A) and the component (C) is promoted by the organoaluminum compound of the component (B). I have. [Detailed Description of the Invention] The method for producing an α-olefin polymer according to the present invention uses a catalyst comprising component (A), component (B) and component (C). Here, “consisting of” does not exclude the coexistence of an arbitrary third component as long as the effect is not deteriorated when the component (A), the component (B) and the component (C) are used. Absent. <Component (A)> Component (A) is represented by the following general formula _{(1): Q a (C} 5 H 5-ab R 4 b) (C 5 H 5-ac R 5 c) MeXY (1) or, following formula _(2): a transition metal compound represented by _{S a (C 5 H 5-} ad R 6 d) ZMeXY (2).

Here, Q represents a binding group bridging the two conjugated five-membered ring ligands, and S represents a binding group bridging the conjugated five-membered ligand and the Z group. Specifically, (a) a methylene group,
A C ₁ -C ₄ alkylene group such as an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group or a cyclohexylene group;
Or its side chain lower alkyl or phenyl substituent,
(B) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group,
Silylene group or oligosilylene group such as tetramethyldisilylene group or its side chain lower alkyl or phenyl substituent, (c) hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, that is, these elements required as a crosslinking group A hydrocarbon group, preferably a lower alkyl group or a phenyl group, or a hydrocarbyloxy group, preferably a lower alkoxy group, specifically a (CH ₃ ) ₂ Ge group, (C ₆ H ₅ )
₂ Ge group, _(CH 3) P _group, (C _{6 H} 5) P group, _{(C 4}
H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B group, (C
₄ H ₉₎ B _group, (C _{6 H} 5) B _{group, (C 6} H 5) Al
Group, (CH ₃ O) Al group and the like. Preferred are an alkylene group and a silylene group. a is 0 or 1;

In the above general formula, (C ₅ H _5-ab R ⁴
_{b), (C 5 H 5} -ac R 5 c) and _{(C 5} H _5-ad R
⁶ _d ) The conjugated five-membered ring ligands represented by b), c and d, and R
^Since the definitions of ⁴ , R ⁵ and R ⁶ are the same (details described later), it goes without saying that these three conjugated five-membered ring groups may be the same or different.

One specific example of this conjugated five-membered ring group is b =
0 (or c = 0, d = 0) is a cyclopentadienyl group (no substituent other than the crosslinking group Q or S).
This conjugated five-membered ring group has b ≠ 0 (or c ≠ 0, d ≠ 0)
Is a group having a substituent, one specific example of R ⁴ (or R ⁵ , R ⁶ ) is a hydrocarbon group (C ₁ to C ₄ ).
C ₂₀ , preferably C ₁ -C ₁₂ ), even if this hydrocarbon group is bonded to a cyclopentadienyl group as a monovalent group, To form a ring together with a part of the cyclopentadienyl group. A typical example of the latter is R ⁴
(Or R ⁵ , R ⁶ ) sharing a double bond of the cyclopentadienyl group to form a fused six-membered ring,
That is, the conjugated five-membered ring group is an indenyl group or a fluorenyl group. That is, typical examples of the conjugated five-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ⁴ , R ⁵ and R ⁶ each represent, in addition to the above-mentioned C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ hydrocarbon group, a halogen group (eg, fluorine, chlorine, bromine), An alkoxy group (for example, _one of C ₁ -C ₁₂ ), a silicon-containing hydrocarbon group (for example, a silicon atom is -Si (R)
(R ′) and (R ″) groups containing about 1 to 24 carbon atoms), a phosphorus-containing hydrocarbon group (for example, a phosphorus atom
(R) a group having about 1 to 18 carbon atoms in the form of (R ′)),
Nitrogen-containing hydrocarbon group (for example, when a nitrogen atom is -N (R)
(R ′)-containing groups having about 1 to 18 carbon atoms) or boron-containing hydrocarbon groups (for example, a boron atom represented by -B
(R) a group having about 1 to 18 carbon atoms contained in the form of (R ')). When b (or c, d) is 2 or more and a plurality of R ⁴ (or R ⁵ , R ⁶ ) are present, they may be the same or different.

B, c and d are such that when a is 0, 0 ≦ b
≦ 5, 0 ≦ c ≦ 5, 0 ≦ d ≦ 5, and when a is 1, 0 ≦
It is an integer satisfying b ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4.

Me is titanium, zirconium and hafnium. Particularly, zirconium is preferable.

Z is oxygen (-O-), sulfur (-S-),
An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms;
A thioalkoxy group having 1 to 20, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a nitrogen-containing hydrocarbon having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Group, having 1 to 40 carbon atoms, preferably 1 to 1
8 is a phosphorus-containing hydrocarbon group.

X and Y are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and an amino group. A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, for example, a diphenylphosphine group), or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, A typical example is a trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferred.

Specific examples of the transition metal compound when Me is zirconium are as follows.

(A) Transition metal compounds having no bridging bonding group and having two conjugated five-membered ring ligands, such as (1) bis (cyclopentadienyl) zirconium dichloride,
(2) bis (methylcyclopentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride,
(5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6) bis (pentamethylcyclopentadienyl) zirconium dichloride, (7) bis (n-butylcyclopentadienyl) zirconium dichloride, (8) bis (Indenyl) zirconium dichloride, (9) bis (fluorenyl) zirconium dichloride, (10) bis (cyclopentadienyl) zirconium monochloride monohydride, (11) bis (cyclopentadienyl) methyl zirconium monochloride, (1
2) bis (cyclopentadienyl) ethyl zirconium monochloride, (13) bis (cyclopentadienyl) phenyl zirconium monochloride, (14) bis (cyclopentadienyl) zirconium dimethyl, (15) bis (cyclopentadiene) Enyl) zirconium diphenyl, (1
6) bis (cyclopentadienyl) zirconium dineopentyl, (17) bis (cyclopentadienyl) zirconium dihydride, (18) (cyclopentadienyl) (indenyl) zirconium dichloride, (19)
(Cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(B) Transition metal compounds having two 5-membered ring ligands bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride,
(3) ethylene bis (indenyl) zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride, (5) ethylene bis (indenyl) zirconium monomethoxy monochloride, (6) ethylene bis (indenyl) zirconium Diethoxide, (7) ethylenebis (indenyl) zirconium dimethyl, (8) ethylenebis (4,5
6,7-tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl) zirconium dichloride, (11) ethylenebis (2,4 -Dimethylindenyl) zirconium dichloride, (12) ethylenebis (2-methyl-4-trimethylsilylindenyl) zirconium dichloride (13)
Ethylene bis (2,4-dimethyl-5,6,7-trihydroindenyl) zirconium dichloride (14) Ethylene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (15) ethylene (2-methyl-4-
tertbutylcyclopentadienyl) (3'-tertbutyl-5'-methylcyclopentadienyl) zirconium dichloride, (16) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (17)
Isopropylidenebis (2-methylindenyl) zirconium dichloride (18) isopropylidenebis (indenyl) zirconium dichloride, (19) isopropylidenebis (2,4-dimethylindenyl) zirconium dichloride, (20) isopropylidene (2, 4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (21) isopropylidene (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl- 5'-methylcyclopentadienyl) zirconium dichloride, (22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (23)
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride hydride, (24) methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) zirconium dimethyl, (25) methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) zirconium diphenyl, (26) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (27) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride , (28) isopropylidene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (29) isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, (30) isopropylidene ( Cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (31) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (32) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium Dichloride, (33) isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (34) isopropylidene (2,5-dimethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (35) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (36) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (37) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (38) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (39) diphenylmethylene (cyclopentadienyl) ( 3,4-diethylcyclopentadienyl) zirconium dichloride, (40) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (41) cyclohexylidene (cyclopentadienyl) (F Oreniru) zirconium dichloride, (42) cyclohexylidene (2,
5-dimethylcyclopentadienyl) (3 ', 4'-dimethyldimethylcyclopentadienyl) zirconium dichloride and the like.

(C) Transition metal compounds having a 5-membered ring ligand of a silylene group, such as (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5,6,7-tetrahydro (Indenyl) zirconium dichloride, (3) dimethylsilylene bis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (5) dimethylsilylene (2,4- Dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (6) phenylmethylsilylenebis (indenyl) zirconium dichloride, (7) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium Dichloride, (8) phenylmethylsilylene bis (2,4-dimethylindenyl) zirconium dichloride (9) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′,
5'-dimethylcyclopentadienyl) zirconium dichloride, (10) phenylmethylsilylene (2,3,5
-Trimethylcyclopentadienyl) (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, (11) phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, (12)
Diphenylsilylenebis (2,4-dimethylindenyl) zirconium dichloride (13) diphenylsilylenebis (indenyl) zirconium dichloride, (14) diphenylsilylenebis (2-methylindenyl) zirconium dichloride (15) tetramethyldisilylenebis ( (Indenyl) zirconium dichloride, (16) tetramethyldisilylene bis (cyclopentadienyl) zirconium dichloride, (17) tetramethyldisilylene (3
-Methylcyclopentadienyl) (indenyl) zirconium dichloride, (18) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (19) dimethylsilylene (cyclopentadienyl) ( Trimethylcyclopentadienyl) zirconium dichloride, (20) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (21) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopenta Dienyl) zirconium dichloride, (2
2) Dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (23) Dimethylsilylene (cyclopentadienyl)
(Tetraethylcyclopentadienyl) zirconium dichloride, (24) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (25)
Dimethylsilylene (cyclopentadienyl) (2,7
-Di-t-butylfluorenyl) zirconium dichloride, (26) dimethylsilylene (cyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, (27) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(28) dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (29) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(30) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (31) diethylsilylene (2-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) Zirconium dichloride, (32) dimethylsilylene (2,
5-dimethylcyclopentadienyl) (2,7-di-t
-Butylfluorenyl) zirconium dichloride, (33)
Dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (34) Dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butyl) (Fluorenyl) zirconium dichloride, (35) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (36) dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride , (37) dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (38)
Dimethylsilylene (diethylcyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride and the like.

(D) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermanium bis (indenyl) zirconium dichloride, 2) dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(3) methyl aluminum bis (indenyl) zirconium dichloride, (4) phenyl aluminum bis (indenyl) zirconium dichloride, (5) phenylphosphinobis (indenyl) zirconium dichloride,
(6) ethylboranobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride, and the like.

(E) Transition metal compounds having one five-membered ring ligand, such as (1) pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride,
(2) indenyl-bis (phenyl) aminozirconium dichloride, (3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, (4) pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) dimethylsilylene ( Tetramethylcyclopentadienyl) phenylaminozirconium dichloride, (6) dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, (7) dimethylsilylene (tetrahydroindenyl) (bis (trimethylsilyl) amino) zirconium dichloride, (8) Dimethylgermane (tetramethylcyclopentadienyl) phenylaminozirconium dichloride and the like are exemplified.

(F) Further, compounds obtained by replacing chlorine in the compounds (a) to (e) with bromine, iodine, hydride, methyl, phenyl and the like can also be used.

Further, in the present invention, a compound in which the central metal of the zirconium compound exemplified in the above (a) to (f) is changed from zirconium to titanium or hafnium can be used as the component (A).

Of these, zirconium compounds, hafnium compounds and titanium compounds are preferred. More preferred are titanium compounds, zirconium compounds, and hafnium compounds cross-linked with an alkylene group or a silylene group. <Component (B)> The component (B) is an organoaluminum compound.

[0034] Specific examples of the organoaluminum compound of component _{^{(B), R 7 3-}} n AlX n or ^{R 8} _3-m Al
(OR ⁹ ) _m (where R ⁷ and R ⁸ may be the same or different and each may be a hydrocarbon residue having about 1 to 20 carbon atoms or a hydrogen atom, and R ⁹ may be a hydrocarbon residue having about 1 to 20 carbon atoms. ,
X is halogen, n and m are each 0 ≦ n <3, 0 <
m <3) or the following general formula (II) or (III)
Some are represented by

[0035]

Embedded image (Where p is a number from 0 to 40, preferably 2 to 25, and R ¹⁰ is a hydrocarbon residue, preferably a carbon number of 1 to 1).
0, particularly preferably 1 to 4 carbon atoms. )
Specifically, (a) trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum;
(B) alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride; (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride;
(D) aluminum alkoxides such as diethylaluminum ethoxide, dimethylaluminum trimethylsiloxide and diethylaluminum phenoxide;
Examples thereof include alumoxanes such as methylalumoxane, ethylalumoxane, isobutylalumoxane, and methylisobutylalumoxane. It is also possible to use a mixture of a plurality of these. Of these, trialkylaluminum, aluminum alkoxide and the like are preferable. Even more preferred are organoaluminum compounds having a methyl group, an ethyl group, and an isoble group. <Component (C)> The component (C) is a compound having the following structure (I).

[0036]

Embedded image (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ² is hydrogen, halogen, a siloxy group, a lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and each of the four R ² may be the same or different. )
The component (C) is a reaction product of the following components (i) and (ii).

Component (i): General formula

[0038]

Embedded image (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms.) Component (ii): an organoaluminum compound. Component (i) Component (i) has the general formula

[0039]

Embedded image (R ¹ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms). Specific examples of such alkylboronic acids include:
Methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, iso-
Examples include butylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. You. Preferred of these are:
Methylboronic acid, iso-butylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. Even more preferred is methylboronic acid. Component (ii) Component (ii) is an organoaluminum compound.

[0040] Specific examples of the organoaluminum compound of component (ii), the general formula R 2 ^_3-q AlX _q or

[0041]

Embedded image Or

[0042]

Embedded image Some are represented by (However, R ² has 1 to 1 carbon atoms.
0 represents a hydrocarbon residue; X represents a hydrogen or a halogen group;
¹¹ represents hydrogen, halogen or a hydrocarbon residue having 1 to 10 carbon atoms, and q represents 0 ≦ q <3. Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, trin-butylaluminum, trin-propylaluminum, triisoprenylaluminum, etc. Alkyl aluminum halides such as alkylaluminum, (b) dimethylaluminum chloride, diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) dimethylaluminum hydride, diethylaluminum hydride, Alkyl alcohols such as diisobutyl aluminum hydride Aluminum hydride, alkyl aluminum siloxides such as (a) dimethyl aluminum (trimethyl siloxide), dimethyl aluminum (trimethyl siloxide) and diethyl aluminum (trimethyl siloxide), and tetra (e) tetraisobutylalumoxane and tetraethylalumoxane. Examples thereof include alkylalumoxane. It is also possible to use a mixture of a plurality of these.

Preferred among these organoaluminum compounds are derivatives of methylaluminum and isobutylaluminum, such as trimethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diisobutylaluminum chloride and diisobutylaluminum hydride. Even more preferred are trimethylaluminum, triisobutylaluminum, and mixtures thereof. Contact ratio between component (i) and component (ii) Component (i) and component (ii) can be used in any reaction ratio.However, in order to efficiently produce the desired reaction product, the components are used. It is preferred that the molar ratio of (i) to component (ii) be 1: 2. In addition, component (i) and component
The reaction (ii) is usually carried out in an inert solvent under an inert gas atmosphere. Various contact methods are possible.
For example, (i) a method in which the component (i) is mixed in a toluene solvent, and then a solution diluted with the component (ii) in toluene is added dropwise to cause a reaction. )
And a method of reacting by supplying the solid as a solid, (c) a method of diluting the component (i) and the component (ii) in toluene, and dropping each of them at a constant speed into another container to cause a reaction. Component (i) and component
The reaction temperature and the reaction time of (ii) are optional, but generally, both components are kept at a low temperature, for example, -78 to 30 ° C, preferably -78 to 10 ° C, since a side reaction is likely to occur due to a rapid reaction.
And then gradually raising the temperature, for example, to -10 to 70 ° C. The reaction time is optional as long as the desired product is obtained, but is generally in the range of 1 minute to 24 hours. <Optional Component> The present invention relates to the production of an α-olefin polymer using a polymerization catalyst comprising component (A), component (B) and component (C). ) And component (C), any component can be used as long as the effects of the present invention are not impaired.
Optional components that can be added include, for example, H ₂ O,
Active hydrogen-containing compounds such as methanol, ethanol and butanol; ethers, esters and electron-donating compounds such as amines; phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and alkoxy-containing compounds such as diphenyldimethoxysilane; Organic boron compounds such as triethylborane, triphenylborane, tris (pentafluorophenyl) borane, and triphenylcarbyltetrakis (pentafluorophenyl) borane can be exemplified. <Formation of Catalyst> The catalyst used in the present invention is prepared by mixing the above components (A), (B) and (C) and optionally the above-mentioned optional components in a polymerization tank or outside the polymerization tank. And in the presence or absence of a monomer to be polymerized.

Component (A), Component (B) used in the present invention
The amount of the component (C) and the amount of the component (C) used are arbitrary, but generally, the atomic ratio (Al / Me) is from 0.01 to 10,000, preferably from 0.1 to 1,000. The amount of the organoaluminum compound used as the component (C) is not limited.
01 to 100,000, preferably 0.1 to 10,000
0, more preferably 2 to 3,000. The contacting method is also optional, and each component may be separately put into the polymerization tank in an arbitrary order during the polymerization, and may be brought into contact with the polymerization tank. Then, you may contact with another component. <Polymerization of α-olefin> The catalyst of the present invention can be applied not only to solvent polymerization using a solvent but also to liquid-phase solventless polymerization, gas-phase polymerization, and melt polymerization substantially using no solvent. Applied. It is applied to continuous polymerization and batch polymerization.

As the solvent in the case of solvent polymerization, hexane, heptane, pentane, cyclohexane, benzene,
A single or mixture of a saturated aliphatic or aromatic hydrocarbon solvent such as toluene is used.

The polymerization temperature is about -78 to 200 ° C, preferably -20 to 100 ° C. The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 50 kg / cm ^2.
-G range. In addition, known means at the time of polymerization,
For example, the molecular weight can be adjusted by selecting the temperature and pressure or by introducing hydrogen.

The α-olefin polymerized by the catalyst of the present invention (including ethylene in the present invention), that is, the α-olefin used in the polymerization reaction in the method of the present invention has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. , Are α-olefins. Specifically, for example, ethylene, propylene,
-Butene, 4-methyl-1-pentene, 1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, particularly preferably ethylene, propylene,
There are 1-butene, 1-hexene and 4-methyl-1-pentene. These α-olefins can be used as a mixture by mixing two or more kinds.

The catalyst of the present invention can also copolymerize the above α-olefins with ethylene. Further, other monomers copolymerizable with the above-mentioned α-olefin, for example, butadiene, 1,4-hexadiene, 1,8-nonadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like Such conjugated and non-conjugated dienes, or cyclopropene, cyclobutene, cyclopentene,
It is also effective for copolymerization of cyclic olefins such as norbornene and dicyclopentadiene.

[0049]

【Example】

<Example-1> Preparation of component (A) Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride was prepared according to the method of J. Orgmet. Chem. (342) 21-29.
1988 and J. Orgmet. Chem. (369) was synthesized according to 359-370 19 89.

Specifically, 5.4 g of bis (indenyl) dimethylsilane was diluted with 150 ml of tetrahydrofuran in a 300 ml flask purged with nitrogen, cooled to −50 ° C. or lower, and then cooled with n-butyllithium (1.6M). / L) 23.6 ml was added dropwise over 30 minutes. After completion of dropping, the temperature is raised to room temperature over 1 hour,
The reaction was performed at room temperature for 4 hours to synthesize a reaction solution A.

Into a 500 ml flask purged with nitrogen, 200 ml of tetrahydrofuran was introduced, and -5
After cooling to below 0 ° C., 4.38 grams of zirconium tetrachloride were slowly introduced. Next, after introducing the entire amount of the reaction solution A, the temperature was slowly raised to room temperature over 3 hours. After reacting at room temperature for 2 hours, the temperature was further raised to 60 ° C. and reacted for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in 100 ml of toluene and distilled off again to obtain 3.86 g of crude crystals of dimethylsilylenebis (indenyl) zirconium dichloride.

Next, the crude crystals were dissolved in dichloromethane 15
0 ml and introduced into a 500 ml autoclave. After introducing 5 g of platinum-carbon (0.5 wt% platinum supported) catalyst, H ₂ = 50 kg / cm ² G, 50
A hydrogenation reaction was carried out at a temperature of 5 ° C. for 5 hours. After the reaction,
After the catalyst was removed by filtration, the solvent was distilled off under reduced pressure, extracted with toluene, and recrystallized to obtain 1.26 g of the target dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride.

Preparation of Component (C) Bis (diisobutylaluminumoxy) methylboron was synthesized according to the following method.

Specifically, 100 ml of sufficiently dehydrated and deoxygenated n-hexane and 3.0 g (50 mmol) of methyl boric acid manufactured by Aldrich Co. were introduced into a 500 ml flask purged with nitrogen.
After cooling to -50 ° C or less, 19.8 g (100 mmol) of triisobutylaluminum was added to n-hexane 1
The solution was diluted to 00 ml and slowly added dropwise over 30 minutes. During the addition, the reaction temperature was maintained at -50 ° C or lower. After completion of the dropping, the temperature was gradually raised to 0 ° C. over 1 hour. During the temperature rise, gas was gradually generated at around -10 ° C, and the reaction proceeded. As the reaction progressed, solid methylboric acid dissolved. After maintaining at 0 ° C. for 2 hours, the temperature was returned to room temperature to complete the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain about 17 g of a liquid compound (C-1). The obtained aluminum compound was diluted with toluene and measured for ²⁷ Al-NMR. As a result, a broad peak having a half width of 12,800 Hz was obtained at 134.9 ppm (see FIG. 1).

The measurement of the NMR spectrum ( ²⁷ Al: 7)
0.4MHz) is 6-7% by weight in terms of aluminum atom
2.5 ml of toluene solution and 0.5 parts of heavy benzene
After mixing with Milliliter, GSX made by JEOL Ltd.
The measurement was performed at 27 ° C. using a -270 type NMR measurement apparatus. The measurement conditions of the ²⁷ Al-NMR spectrum were as follows: pulse width 90 °, pulse interval 0.06 seconds, integration number 10,000 times, measurement in non-decoupling mode, ²⁷ A
The chemical shift is determined by the [Al
(H ₂ O) ₆ ] ³⁺ ion was used as an external standard (0 ppm).
For the half width of the spectrum, the peak width at half the height of the maximum value of the peak was converted into Hz.

Polymerization of Ethylene A sufficiently dehydrated and deoxygenated toluene 50 was placed in a 1.5 liter stainless steel autoclave equipped with a stirring and temperature controller, which had been sufficiently replaced with ethylene gas.
0 ml of the component (C-
1) was added to 2 mmol in terms of aluminum atom, 36 mg of trimethylaluminum, and then 0.91 mg (2 μmol) of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride synthesized above, and 100 ml of hydrogen was introduced. The temperature was raised, and polymerization was carried out at 75 ° C. and 7 kg / cm ² G for 2 hours. After completion of the polymerization, the slurry was taken out in 3 liters of ethanol, and the polymer was separated by filtration and dried.
10.3 grams of polymer were obtained. Therefore, the catalytic activity is 120.9 kg polymer / g-component (A), and the MI
(190 ° C.) = 536 g / 10 minutes. <Example-2> The amount of trimethylaluminum used was set at 7.
The polymerization of ethylene was carried out under the same conditions as in Example 1 except that the amount of component (C-1) was 2 mmol and the amount of component (C-1) was 1 mmol. Table 1 shows the results. Comparative Examples 1 and 2 Ethylene was polymerized under the same conditions as in Example 1 except that the component (C-1) or trimethylaluminum was not used. Table 1 shows the results. <Comparative Examples-3, 4> All of the same as Example-1 except that tetraisobutylalumoxane (manufactured by Schering) or polyisobutylalumoxane (manufactured by Tosoh Akzo) was used instead of component (C-1). Polymerization of ethylene was carried out under the conditions. Table 1 shows the results. Incidentally, ²⁷ Al of tetraisobutylalumoxane and polyisobutylalumoxane
-The result of NMR is shown in FIG.2 and FIG.3. <Examples-3 and 4> Instead of using 36 mg of trimethylaluminum, 3
Example 2 except that 3.7 mg or 59.4 mg of triisobutylaluminum was used.
Polymerization of ethylene was carried out under the same conditions as described above. Table 1 shows the results. <Example-5> Bis (dimethylaluminumoxy) methylboron (C-2) was synthesized by a method similar to Example-1. That is, in the production of the component (C) of Example-1, the same conditions as in Example-1 were used except that 7.2 g of trimethylaluminum was diluted in 100 ml of toluene and used instead of 19.8 g of triisobutylaluminum. Was synthesized. Incidentally, ²⁷ Al-N bis (dimethyl oxy) Mechiruhou element (C-2)
FIG. 4 shows the results of the MR.

Polymerization of Ethylene Component (C-2) obtained above was converted to aluminum atom by 2
Except for using mmol, ethylene polymerization was carried out under the same conditions as in Example 1.

95.5 grams of polymer were obtained. Therefore, the catalyst activity is 104.7 kg polymer / g component (A),
The activity per aluminum atom was 1,410 g polymer / g Al atom, and the MI was 388. <Example-6> Production of component (A) Production of dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl In a 300 ml flask sufficiently purged with nitrogen,
100 ml of dehydrated and degassed diethyl ether, 0.912 of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride obtained in Example-1
Grams were introduced and cooled to below -50 ° C. Then 1.5
4 ml (6 mmol) of methyllithium diluted in M diethyl ether was rediluted to 10 ml of diethyl ether and diluted for 15 minutes. After the feed was completed, the temperature was raised to −10 ° C. over 1 hour, and the reaction was performed while heating to 10 ° C. over 2 hours. After completion of the reaction, diethyl ether was distilled off at 0 to 10 ° C., and then dehydrated and degassed n-
50 ml of pentane was added and stirred for 10 minutes.
After removing the solid by filtration, the solvent was distilled off until the supernatant solution was about 10 ml, and then left in a freezer overnight.
White crystals were obtained. The crystals were separated, washed with a small amount of pentane, and dried to obtain 0.65 g of dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl.

Polymerization of Propylene Into a 1.5 liter stainless steel autoclave equipped with a stirring and temperature controller sufficiently replaced with propylene gas, fully dehydrated and deoxygenated toluene 5 was added.
00 ml, the same components (C
-1) 2 mmol and trimethylaluminum 3
6.0 milligrams were introduced, and then 0.84 milligrams (2 .mu.mol) of the dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl obtained above was introduced.
Polymerization was carried out at 0 ° C. for 7 kg / cm ² G for 2 hours. After completion of the polymerization, the slurry was taken out in 3 liters of methanol to sufficiently precipitate the polymer, followed by filtration and drying.
22.3 grams of polymer were recovered. Therefore, the catalytic activity was 24.4 kg polymer / g component (A). The number average molecular weight of the polymer was 12,600, the molecular weight distribution (weight average molecular weight / number average molecular weight) was 1.95, and the melting point of the polymer was 121 ° C. <Comparative Example-5> Propylene was polymerized under the same conditions as in Example-6 except that trimethylaluminum was not used in Example-6. Table 2 shows the results. <Example-7> Production of component (C) In producing component (C) of Example-1, instead of 19.8 g of triisobutylaluminum, 9.9 g of triisobutylaluminum and 3.6 g of trimethylaluminum were used. Was reacted in the same manner as in Example 1 except that the reaction was carried out using a mixture diluted with 100 ml of toluene. As a result, 12.2 g of the liquid compound (C-3) was obtained.

Polymerization of Propylene Propylene was polymerized under the same conditions as in Example 6 except that 2 mmol of the component (C-3) obtained above was used. Table 2 shows the results. <Examples 8, 9 and Comparative Example 6> In the polymerization of propylene in Example 7, instead of 36.0 milligrams of trimethylaluminum, triethylaluminum was used instead of 36.0 mg.
3 milligrams or triisobutylaluminum 5
Polymerization of propylene was carried out under the same conditions as in Example 7 except that 9.4 mg was used or not used. Table 2 shows the results. <Example-10> Production of component (A) Synthesis of dimethylsilylene (tetramethylcyclopentadienyl) tert-butylaminotitanium dichloride In a 300 ml flask sufficiently purged with nitrogen,
Dehydrated and degassed tetrahydrofuran (THF) 100
Milliliter and add it to Kanto Chemical Co., Ltd. (tert
2.52 grams (10 mmol) of -butyramide) (tetramethylcyclopentadienyl) dimethylsilane were dissolved. Then, after cooling this to −50 ° C. or less,
13.4 ml (20 mmol) of methyllithium diluted to 1.5 M with diethyl ether was introduced over 10 minutes. Then, the temperature was raised to room temperature over 1 hour, and the reaction was carried out at room temperature for 6 hours. After the completion of the reaction, the solvent was distilled off, followed by washing with THF several times to obtain 2.16 g of dilithium (tert-butylamide) (tetramethylcyclopentadienyl) dimethylsilane.

Next, 100 ml of dehydrated and deoxygenated diethyl ether and 0.38 titanium tetrachloride were placed in a 300 ml flask sufficiently purged with nitrogen.
Grams (2 mmol) were mixed below -50 <0> C. Next, 2 millimoles (0.53 grams) of the dilithium (tert-butylamide) (tetramethylcyclopentadienyl) dimethylsilane obtained above diluted in 10 milliliters of tetrahydrofuran was added to -50 ° C or lower. For 30 minutes. After completion of the dropping, the temperature was raised to room temperature over 1 hour, and the reaction was carried out at room temperature for 24 hours. After the reaction,
After the solvent was distilled off, 50 ml of toluene was added, and lithium chloride was removed by filtration. Then, toluene was distilled off, and 30 ml of n-pentane was added to dissolve the solution, and then stored in a refrigerator for 24 hours. As a result, 0.25 g of yellow crystals of dimethylsilylene (tetramethylcyclopentadienyl) tert-butyl was obtained as yellow crystals. Amido titanium dichloride was obtained.

Polymerization of Ethylene Polymerization of ethylene was carried out under the same conditions as in Example 1 except that the above component (A) was used. As a result, 33.8
Grams of polymer were obtained. Therefore, the catalytic activity is 45.
9 kg polymer / gram component (A), MI is 152 g
/ 10 minutes, the melting point of the polymer was 132.0 ° C.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

Industrial Applicability According to the present invention, the catalytic activity per aluminum atom is largely improved, expensive alumoxane compounds are not required, and the use of an aromatic hydrocarbon solvent which is an industrial constraint is not required. Is as described above in the section of “Summary of the Invention”.

[Brief description of the drawings]

FIG. 1 is a ²⁷ Al-NMR diagram of bis (diisobutylaluminoxy) methylboron produced in Example-1.

FIG. 2 is a ²⁷ Al-NMR diagram of tetraisobutylalumoxane (manufactured by Schering) used in Comparative Example-3.

FIG. 3 is a ²⁷ Al-NMR diagram of polyisobutylalumoxane (manufactured by Tosoh Akzo) used in Comparative Example-4.

FIG. 4 is a ²⁷ Al-NMR diagram of bis (dimethylaluminumoxy) methylboron produced in Example-5.

FIG. 5 is to assist in understanding the technical content of the present invention regarding the Ziegler catalyst.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-172439 (JP, A) JP-A-2-256686 (JP, A) JP-A-62-281882 (JP, A) JP-A-3-3 62806 (JP, A) JP 48-7867 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] 1. A process for producing an α-olefin polymer, which comprises contacting an α-olefin with a catalyst comprising the following components (A), (B) and (C) to polymerize it. Component (A): general formula (1) or the transition metal compound represented by _{(2), Q a (C} 5 H 5-ab R 4 b) (C 5 H 5-ac R 5 c) MeXY ( _{1) S a (C 5 H} 5-ad R 6 d) ZMeXY (2) ( _{where, (C 5 H 5-ab} R 4 b), (C 5 H 5-ac R 5
_c ) and (C ₅ H _5-ad R ⁶ _d ) are each a conjugated 5-membered ring ligand coordinated to Me (R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon residue having 1 to 20 carbon atoms; A halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group (R ⁴ ,
R ⁵ and R ⁶ may be the same or different, and a plurality of R ⁴ , R ⁵ and R ⁶ may be bonded to each other), and Q is a bridge between two conjugated five-membered ligands. A binding group selected from the group consisting of an alkylene group, a silylene group, and a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, where S is a conjugated five-membered ring ligand and a Z group An alkylene group, a silylene group, and germanium, phosphorus,
What is selected from the group consisting of hydrocarbon groups containing nitrogen, boron or aluminum, Z is oxygen, sulfur, an alkoxy group, a thioalkoxy group, a silicon-containing hydrocarbon group,
A nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, Me is titanium, zirconium and hafnium, and X and Y are each a hydrogen, halogen group, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing Hydrocarbon group (X and Y may be the same or different)
A represents 0 or 1, b represents an integer of 0 ≦ b ≦ 5, c represents an integer of 0 ≦ c ≦ 5, and d represents an integer of 0 ≦ d ≦ 5. ) Component (B): an organoaluminum compound, Component (C): a compound having the following structure. Embedded image (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ² is hydrogen, halogen, a siloxy group, a lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and each of the four R ² may be the same or different. ) 2. A method for producing an α-olefin polymer, which comprises contacting an α-olefin with a catalyst comprising the following components (A), (B) and (C) to polymerize it. Component (A): general formula (1) or the transition metal compound represented by _{(2), Q a (C} 5 H 5-ab R 4 b) (C 5 H 5-ac R 5 c) MeXY ( _{1) S a (C 5 H} 5-ad R 6 d) ZMeXY (2) ( _{where, (C 5 H 5-ab} R 4 b), (C 5 H 5-ac R 5
_c ) and (C ₅ H _5-ad R ⁶ _d ) are each a conjugated 5-membered ring ligand coordinated to Me (R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon residue having 1 to 20 carbon atoms; A halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group (R ⁴ ,
R ⁵ and R ⁶ may be the same or different, and a plurality of R ⁴ , R ⁵ and R ⁶ may be bonded to each other), and Q is a bridge between two conjugated five-membered ligands. A binding group selected from the group consisting of an alkylene group, a silylene group, and a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, where S is a conjugated five-membered ring ligand and a Z group An alkylene group, a silylene group, and germanium, phosphorus,
What is selected from the group consisting of hydrocarbon groups containing nitrogen, boron or aluminum, Z is oxygen, sulfur, an alkoxy group, a thioalkoxy group, a silicon-containing hydrocarbon group,
A nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, Me is titanium, zirconium and hafnium, and X and Y are each a hydrogen, halogen group, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing Hydrocarbon group (X and Y may be the same or different)
A represents 0 or 1, b represents an integer of 0 ≦ b ≦ 5, c represents an integer of 0 ≦ c ≦ 5, and d represents an integer of 0 ≦ d ≦ 5. ) Component (B): an organoaluminum compound, Component (C): a reaction product of the following components (i) and (ii). Component (i): (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms.) Component (ii): an organoaluminum compound.