JPH06172438A - Production of alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer without using an expensive alumoxane because of high activity of catalyst per aluminum atom by using a specific transition metal compound, an organoaluminum compound and a specific organoaluminum compound. CONSTITUTION:An alpha-olefin is brought into contact with a catalyst comprising (A) a transition metal compound of group IVB-VIB of the periodic table containing a conjugated five-membered ring ligand [preferably bis(cyclopentadienyl)zirconium dichloride], (B) an organoaluminum compound (preferably trimethylaluminum) and (C) a compound of the formula (R<1> is l-10C hydrocarbon R<2> is ethylene, propylene, etc.) to give the objective polymer. Bis(diisobutylaluminumoxy)methylboron obtained by reacting methylboronic acid with methylisobutylaluminum is preferable as the component C. The polymerization temperature and pressure of the alpha-olefin are preferably -20 to 100 deg.C and atmospheric pressure to 50kg/cm<2>, respectively.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a method for producing an α-olefin polymer. More specifically, the present invention comprises a specific transition metal compound component (component (A)), an ordinary 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 the catalyst.

[0002]

2. Description of the Related Art A method for producing a poly .alpha.-olefin by combining an alumoxane and a transition metal compound is well known (Japanese Patent Laid-Open Nos. 58-45205 and 58-19.
No. 309, No. 60-35007, No. 61-13031
No. 4, No. 62-230802, No. 63-142004
No. 63-234009, No. 64-51408 and No. 64-66214). However, these techniques are considered to have an industrial problem because the activity per aluminum atom is low and thus the production cost is high, and a large amount of aluminum remains in the olefin polymer.

Various proposals have been made for the purpose of solving these problems (Japanese Patent Laid-Open Nos. 61-2111307 and 6-61).
3-130601, 64-16803, JP-A-2
-22308 and 2-167307).
By these proposals, the activity per aluminum is slightly improved, but since such alumoxane has poor solubility and is difficult to handle and it is difficult to remove aluminum, the quality of the olefin polymer is deteriorated and the hue is deteriorated. It is considered to be the cause of this and further improvement is necessary.

As another proposal, there is a method in which other organoaluminum compounds and the like coexist in methylalumoxane (Japanese Patent Laid-Open Nos. 60-260602 and 60-13060).
No. 4, No. 63-89506, No. 63-178108.
No. 63-218707, No. 64-9206, JP-A No. 1-315407, No. 2-22306, and No. 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, a catalyst component for olefin polymerization comprising an alumoxane compound having two or more kinds of alkyl groups has been proposed (JP-A-2-247).
No. 201, No. 2-250886, No. 4-46906
Nos. 4-26410 and 4-266910). Further, there is also a proposal to use an alumoxane compound in which a part of the alkyl group of such an alumoxane compound is converted to hydrogen (Japanese Patent Laid-Open No. 3-139503).
However, all of these alumoxane compounds have a high degree of association and must be used in a large amount in order to maintain high activity, and since they are soluble only in an aromatic solvent, they are an industrial constraint. There are many.

On the other hand, as an attempt to reduce the molecular weight of the polymer,
A proposal has been made to use a tetraalkylalumoxane compound (Japanese Patent Laid-Open No. 3-197514). This alumoxane compound is advantageous in that it is easily dissolved in an aliphatic hydrocarbon solvent, but although it exhibits activity in ethylene polymerization, it seems that the polymerization activity of α-olefins such as propylene is 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 (JP-A-2-
No. 256686, No. 4-304202, No. 4-304
Nos. 203 and 4-304206). But,
The product obtained by these methods is an alumoxane having an Al-O-Al bond, and it seems to have the same problems as described above.

On the other hand, as an organoaluminum compound other than an alumoxane compound, a reaction product of a divalent alcohol or a divalent amine with an organoaluminum compound has been proposed (JP-A-3-62806). However, since the organoaluminum compound obtained by this reaction can usually obtain a remarkably low polymerization activity when combined with a metallocene compound, it is not sufficient as a substitute compound for the alumoxane compound, and further improvement is desired. [Outline of Invention]

[0009]

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

[0010]

[Means for Solving the Problems]

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

That is, in the method for producing an α-olefin polymer according to the present invention, an α-olefin is brought into contact with a catalyst composed of the following components (A), (B) and (C) to polymerize it. It is a feature.

Component (A): Transition metal compound of group IVB to VIB of the periodic table having at least one conjugated five-membered ring ligand, component (B): organoaluminum compound, component (C): Having compounds.

[0013]

[Chemical 3] (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ² is hydrogen, halogen, siloxy group, lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and four R ² may be the same or different. ) Further, another method for producing an α-olefin polymer according to the present invention is to polymerize by contacting an α-olefin with a catalyst consisting of the following components (A), (B) and (C): It is characterized by.

Component (A): transition metal compound of group IVB to VIB of the periodic table having at least one conjugated five-membered ring ligand, component (B): organoaluminum compound, component (C): the following component ( Reaction products of i) and component (ii).

Component (i):

[0016]

[Chemical 4] (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, the catalytic activity per aluminum atom is significantly improved, an expensive alumoxane compound is not required, and an aromatic carbonization which is an industrial constraint It is also unnecessary to use a hydrogen solvent. Although the reason why the effects of the present invention are expressed has not been clarified yet, it is presumed that it is because the organoaluminum compound of the component (B) promotes the formation of active sites by the components (A) and (C). There is. [Detailed Description of the Invention] The method for producing an α-olefin polymer according to the present invention uses a catalyst comprising a component (A), a component (B) and a component (C). Here, "consisting of" means component (A), component (B) and component (C).
The use of does not exclude the coexistence of an optional third component as long as the effect is not deteriorated. <Component (A)> The component (A) is a transition metal compound of Group IVB to VIB of the periodic table having at least one conjugated five-membered ring ligand. Specifically, 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 the following general formula (2): S There is a transition metal compound represented by _a (C ₅ H _5-ad R ⁶ _d ) ZMeXY (2).

Here, Q represents a bonding group bridging the two conjugated five-membered ring ligands, and S represents a bonding group bridging the conjugated five-membered ring ligand and the Z group. For details, (a) methylene group,
An ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group or other C ₁ -C ₄ alkylene group or a cyclohexylene group,
Or its side chain lower alkyl or phenyl substitution product,
(B) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group,
A silylene group such as a tetramethyldisilylene group or an oligosilylene group or a side chain lower alkyl or phenyl substituent thereof, (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, that is, these elements necessary as a bridging group A hydrocarbon group excluding the divalent valence of, preferably a lower alkyl group or a phenyl group, or a hydrocarbyloxy group, preferably a lower alkoxy group, specifically, (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, a (CH ₃ O) Al group, and the like. Preferred are alkylene groups and silylene groups. 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
^The conjugated five-membered ring ligand represented by ⁶ _d ) is defined separately, but is not limited to b, c and d, and R.
It is needless to say that the three conjugated five-membered ring groups may be the same or different since the definitions themselves of ⁴ , R ⁵ and R ⁶ are the same (details will be given later).

One specific example of this conjugated five-membered ring group is b =
0 (or c = 0, d = 0) cyclopentadienyl group (no substituent other than the bridging group Q or S).
This conjugated five-membered ring group is b ≠ 0 (or c ≠ 0, d ≠ 0)
And one having a substituent, one specific example of R ⁴ (or R ⁵ , R ⁶ ) is a hydrocarbon group (C _1- ).
C _20, preferably a C ₁ -C _12), the hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and two of which are when it is present a plurality May be bonded at the other end to form a ring with a part of the cyclopentadienyl group. A typical example of the latter is R ⁴
(Or R ⁵ , R ⁶ ) share a double bond of the cyclopentadienyl group to form a condensed 6-membered ring,
That is, the conjugated 5-membered ring group is an indenyl group or a fluorenyl group. That is, typical examples of the conjugated 5-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ⁴ , R ⁵ and R ⁶ are each a halogen group (for example, fluorine, chlorine or bromine) in addition to the above C _{1 to} C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon group. Alkoxy groups (for example, those of C _{1 to} C ₁₂ ), silicon-containing hydrocarbon groups (for example, silicon atom to -Si (R))
(R ′) (R ″) in the form of a group having about 1 to 24 carbon atoms, and a phosphorus-containing hydrocarbon group (for example, a phosphorus atom is —P
(A group having about 1 to 18 carbon atoms in the form of (R) (R ')),
A nitrogen-containing hydrocarbon group (for example, a nitrogen atom is -N (R)
(R ') group containing about 1 to 18 carbon atoms or a boron-containing hydrocarbon group (for example, a boron atom containing -B).
(R) is a group having about 1 to 18 carbon atoms 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 0 ≦ b when a is 0
≦ 5, 0 ≦ c ≦ 5, 0 ≦ d ≦ 5, and when a is 1, 0 ≦
It is an integer that satisfies b ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4.

Me is a transition metal of Groups IVB to VIB of the Periodic Table, preferably titanium, zirconium and hafnium. Zirconium is particularly 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 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a nitrogen-containing hydrocarbon group 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, and an amino group. , A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 (specifically, for example, diphenylphosphine group), or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 (specifically, Specifically, for example, a trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferable.

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

(A) A transition metal compound having no conjugated cross-linking group and two conjugated five-membered ring ligands, for example (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) methylzirconium monochloride, (1)
2) Bis (cyclopentadienyl) ethyl zirconium monochloride, (13) Bis (cyclopentadienyl) phenyl zirconium monochloride, (14) Bis (cyclopentadienyl) zirconium dimethyl, (15) Bis (cyclopentadienyl) (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) a transition metal compound having two five-membered ring ligands bridged with an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride,
(3) ethylenebis (indenyl) zirconium monohydride monochloride, (4) ethylenebis (indenyl) methylzirconium monochloride, (5) ethylenebis (indenyl) zirconium monomethoxymonochloride, (6) ethylenebis (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-
tert-butylcyclopentadienyl) (3'-tert-butyl-5'-methylcyclopentadienyl) zirconium dichloride, (16) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (17)
Isopropylidene bis (2-methylindenyl) zirconium dichloride (18) Isopropylidene bis (indenyl) zirconium dichloride, (19) Isopropylidene bis (2,4-dimethylindenyl) zirconium dichloride, (20) Isopropylidene (2,2) 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) A transition metal compound having a silylene group-bridged five-membered ring ligand, for example, (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, (3) dimethylsilylene bis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylene bis (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) Tetramethyldisilirenebis ( Indenyl) zirconium dichloride, (16) tetramethyldisilirene bis (cyclopentadienyl) zirconium dichloride, (17) tetramethyldisilirene (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) dimethyl silylene (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) dimethyl germanium (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(3) methyl aluminum bis (indenyl) zirconium dichloride, (4) phenyl aluminum bis (indenyl) zirconium dichloride, (5) phenylphosphino bis (indenyl) zirconium dichloride,
Examples include (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, for example (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) Examples include dimethylgermane (tetramethylcyclopentadienyl) phenylaminozirconium dichloride and the like.

(F) Further, it is also possible to use the compounds (a) to (e) in which chlorine is replaced by bromine, iodine, hydride, methyl, phenyl or the like.

Further, in the present invention, the central metal of the zirconium compound exemplified in the above (a) to (f) as the component (A) is zirconium to titanium, hafnium, niobium,
A compound in which molybdenum, tungsten or the like is replaced can also be used.

Of these, preferred are zirconium compounds, hafnium compounds and titanium compounds. Even more preferred are titanium compounds, zirconium compounds and hafnium compounds crosslinked with alkylene or silylene groups. <Component (B)> The component (B) is an organoaluminum compound.

Specific examples of the organoaluminum compound as the component (B) include R ⁷ _3-n AlX _n or R ⁸ _3-m Al.
(OR ⁹ ) _m (wherein R ⁷ and R ⁸ may be the same or different and are a hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms, and R ⁹ is a hydrocarbon residue having about 1 to 20 carbon atoms. ,
X is halogen, and n and m are 0 ≦ n <3 and 0 <, respectively.
m <number of 3) or the following general formula (II) or (III)
Some are represented by.

[0035]

[Chemical 5] (Here, p is a number of 0 to 40, preferably 2 to 25, R ¹⁰ is a hydrocarbon residue, preferably 1 to 1 carbon atoms.
0, particularly preferably having 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) Diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, alkyl aluminum halides such as ethyl aluminum dichloride, (c) diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride,
(D) Aluminum alkoxides such as diethylaluminum ethoxide, dimethylaluminum trimethylsiloxide, and diethylaluminum phenoxide, (e)
Examples 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 and aluminum alkoxide are preferable. More preferred are organoaluminum compounds having a methyl group, an ethyl group, and an isoburu group. <Component (C)> The component (C) is a compound having the following structure (I).

[0036]

[Chemical 6] (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ² is hydrogen, halogen, siloxy group, lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and 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]

[Chemical 7] (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms.) Component (ii): an organoaluminum compound. Component (i) Component (i) is the general formula

[0039]

[Chemical 8] Is an alkylboronic acid represented by (R ¹ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms). Specific examples of such an alkylboronic acid 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. It Of these, the preferred one is
Examples include methylboronic acid, iso-butylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. More preferred is methylboronic acid. Component (ii) Component (ii) is an organoaluminum compound.

Specific examples of the organoaluminum compound of the component (ii) include those represented by the general formula R ² _3-q AlX _q or

[0041]

[Chemical 9] Or

[0042]

[Chemical 10] Some are represented by. (However, R ² has 1 to 1 carbon atoms.
A hydrocarbon residue of 0, X is hydrogen or a halogen group, R is
¹¹ represents hydrogen, halogen or a hydrocarbon residue having 1 to 10 carbon atoms, and q represents 0 ≦ q <3. ) Specifically, (a) trialuminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisoprenylaluminum, etc. Alkyl aluminum, (b) dimethyl aluminum chloride, diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, alkyl aluminum halides such as ethyl aluminum dichloride, (ha) dimethyl aluminum hydride, diethyl aluminum hydride, Alkyl Al such as Diisobutyl Aluminum Hydride Alkyl aluminum siloxides such as aluminum hydride, (d) dimethyl aluminum (trimethyl siloxide), dimethyl aluminum (trimethyl siloxide), and diethyl aluminum (trimethyl siloxide), tetra (e) tetraisobutyl alumoxane, tetraethyl alumoxane, etc. An alkyl alumoxane etc. are illustrated. 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 trimethylaluminium, triisobutylaluminum, and mixtures thereof. The contact ratio between the component (i) and the component (ii) The component (i) and the use ratio in the case of reacting the component (ii) are arbitrary, but in order to efficiently produce the desired reaction product, the component It is preferable that the molar ratio of (i) to component (ii) is 1: 2. Also, the component (i) and the component
The reaction (ii) is usually carried out in an inert solvent under an inert gas atmosphere. Various contact methods can be used.
For example, (a) a method in which the component (i) is mixed in a toluene solvent, and then a toluene diluted solution of the component (ii) is added dropwise to react, and (b) the component (ii) is diluted in the hexane diluted solution. )
Examples thereof include a method of supplying and reacting 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 rate into another container to react. Component (i) and component
The reaction temperature and reaction time of (ii) are arbitrary, but in general, since a side reaction is likely to occur due to a rapid reaction, both components are kept at a low temperature, for example, -78 to 30 ° C, preferably -78 to 10 ° C.
The method of gradually raising the temperature, for example, -10 to 70 [deg.] C. after mixing in [1] is preferable. The reaction time is arbitrary as long as the desired product is obtained, but it is generally carried out 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.
As an optional component that can be added, for example, H ₂ O,
Active hydrogen-containing compounds such as methanol, ethanol, butanol, electron-donating compounds such as ethers, esters, amines, phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, alkoxy-containing compounds such as diphenyldimethoxysilane, Examples thereof include organic boron compounds such as triethylborane, triphenylborane, tris (pentafluorophenyl) borane and triphenylcarbyltetrakis (pentafluorophenyl) borane. <Catalyst formation> The catalyst used in the present invention comprises the above-mentioned component (A), component (B) and component (C) and, if necessary, the above-mentioned optional components inside the polymerization tank or outside the polymerization tank. It can be obtained by contacting in the presence or absence of a monomer to be polymerized.

Component (A) and component (B) used in the present invention
The amount of the component (C) used is arbitrary, but in general, the atomic ratio (Al / A) of the transition metal atom (Me) of the component (A) to the aluminum atom in the organoaluminum compound of the component (B). Me) is 0.01 to 10,000, preferably 0.1 to 1,000. Further, the amount of the organoaluminum compound of the component (C) used is also arbitrary, but generally, the atomic ratio (Al / Me) to the transition metal atom of the component (A) is 0.
01-100,000, preferably 0.1-10,000
It is 0, more preferably 2 to 3,000. The contacting method is also optional, and each component may be separately placed in the polymerization tank and contacted in the polymerization tank in an arbitrary order during the polymerization. Therefore, it may be brought into contact with other components. <Polymerization of α-Olefin> The catalyst of the present invention can be applied not only to solvent polymerization using a solvent but also to solvent-free liquid phase solventless polymerization, gas phase polymerization and melt polymerization. Applied. It is also applied to continuous polymerization and batch polymerization.

As the solvent in the case of solvent polymerization, hexane, heptane, pentane, cyclohexane, benzene,
Saturated aliphatic or aromatic hydrocarbon solvents such as toluene may be used alone or as a mixture.

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 normal pressure to 50 kg / cm ²
-G range. In the polymerization, known means,
For example, the molecular weight can be controlled by selecting the temperature and pressure or introducing hydrogen.

The α-olefin (including ethylene in the present invention) polymerized by the catalyst of 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. Is an α-olefin. Specifically, for example, ethylene, propylene, 1
-Butene, 4-methyl-1-pentene, 1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., particularly preferably ethylene, propylene,
There are 1-butene, 1-hexene and 4-methyl-1-pentene. These α-olefins may be mixed for use in polymerization.

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

[0049]

【Example】

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

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

200 ml of tetrahydrofuran was introduced into a 500 ml flask which had been purged with nitrogen.
After cooling to below 0 ° C., 4.38 grams of zirconium tetrachloride was slowly introduced. Then, after the entire amount of the reaction solution A was introduced, the temperature was slowly raised to room temperature over 3 hours. After reacting for 2 hours at room temperature, 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, the residue was dissolved in 100 ml of toluene and redistilled to obtain 3.86 g of dimethylsilylenebis (indenyl) zirconium dichloride crude crystal.

Then, this crude crystal was mixed with dichloromethane 15
It was dissolved in 0 ml and introduced into a 500 ml autoclave, and after introducing 5 g of a platinum-carbon (0.5% by weight platinum supported) catalyst, H ₂ = 50 kg / cm ² G, 50
The hydrogenation reaction was carried out for 5 hours under the condition of ° C. After the reaction,
After the catalyst was filtered off, the solvent was distilled off under reduced pressure, the residue was extracted with toluene and then recrystallized to obtain 1.26 g of a 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 methylboric acid manufactured by Aldrich Co. were introduced into a 500 ml flask replaced with nitrogen.
After cooling to -50 ° C or lower, 19.8 g (100 mmol) of triisobutylaluminum was added to n-hexane 1
It was diluted to 00 ml and slowly added dropwise over 30 minutes. The reaction temperature was kept below -50 ° C during the dropping. After the dropping was completed, the temperature was gradually raised to 0 ° C. over 1 hour. During the temperature rising, gas was gradually generated at around −10 ° C. and the reaction proceeded. As the reaction proceeded, 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, and as a result, about 17 g of a liquid compound (C-1) was obtained. As a result of diluting the obtained aluminum compound in toluene and measuring ²⁷ Al-NMR, a broad peak having a half width of 12,800 Hz was obtained at 134.9 ppm (see FIG. 1).

Measurement of NMR spectrum ( ²⁷ Al: 7
0.4MHz) is 6 to 7% by weight in terms of aluminum atom
2.5 ml of toluene solution and 0.5 of heavy benzene
After mixing with milliliter, GSX manufactured by JEOL Ltd.
It is a value measured at 27 ° C. using a -270 type NMR measuring device. ²⁷ measurement conditions Al-NMR spectra, the pulse width 90 °, 0.06-second pulse interval, the number of integrations 10,000, measured in non-decoupling mode, ²⁷ A
l Chemical shift is [Al in aqueous solution of aluminum sulfate
The (H ₂ O) ₆ ] ³⁺ ion was used as an external standard (0 ppm).
The half-width of the spectrum was obtained by converting the peak width at a height half the maximum value of the peak in Hz.

Polymerization of ethylene To a fully autoclaved stainless steel autoclave with an internal volume of 1.5 liter, which was fully replaced with ethylene gas and was equipped with a stirring and temperature control device, toluene 50 that had been thoroughly dehydrated and deoxygenated was used.
0 ml, the component of the present invention (C-
2 mmol of aluminum atom, 36 milligrams of trimethylaluminum, and then 0.91 milligram (2 micromoles) of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride synthesized above were added, and 100 milliliters of hydrogen was introduced. Then, the temperature was raised, and a polymerization operation was performed for 2 hours under the conditions of 75 ° C. and 7 kg / cm ² G. After completion of the polymerization, the slurry was taken out into 3 liters of ethanol, 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),
(190 ° C.) = 536 g / 10 minutes. <Example-2> The amount of trimethylaluminum used was 7.
Polymerization of ethylene was carried out under the same conditions as in Example 1 except that the amount of the component (C-1) used was 2 milligrams and the amount of the component (C-1) used was 1 mmol. Table 1 shows the results. <Comparative Examples-1, 2> Ethylene was polymerized under the same conditions as in Example-1, except that the component (C-1) or trimethylaluminum was not used. The results are shown in Table 1. <Comparative Examples-3 and 4> All the same as Example-1 except that tetraisobutylalumoxane (manufactured by Schering) or polyisobutylalumoxane (manufactured by Tosoh Akzo) is used instead of the component (C-1). Polymerization of ethylene was carried out under the conditions. The results are shown in Table 1. Incidentally, tetra isobutyl alumoxane and polyisobutyl alumoxane of ²⁷ Al
-The result of NMR is shown in FIG. 2 and FIG. Examples 3 and 4 Instead of using 36 milligrams of trimethylaluminum, triethylaluminum
Example-2 except that 3.7 mg or 59.4 mg triisobutylaluminum was used.
Polymerization of ethylene was carried out under the same conditions as above. The results are shown in Table 1. <Example-5> Bis (dimethylaluminumoxy) methylboron (C-2) was synthesized by the method according 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 to 100 ml of toluene and used instead of 19.8 g of triisobutylaluminum. Synthesized in. In addition, ²⁷ Al-N of bis (dimethylaluminumoxy) methylboron (C-2)
The result of MR is shown in FIG.

Polymerization of Ethylene The component (C-2) obtained above was converted into aluminum atom in terms of 2
Polymerization of ethylene was carried out under the same conditions as in Example 1 except that mmol was used.

95.5 grams of polymer were obtained. Therefore, the catalytic activity is 104.7 kg polymer / g component (A),
The activity per aluminum atom was 1,410 g polymer / g Al atom, and MI was 388. <Example-6> Production of component (A) Production of dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl In a 300 ml flask which had been sufficiently replaced with nitrogen,
100 ml of dehydrated and degassed diethyl ether, and 0.912 of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride obtained in Example-1
Gram was introduced and cooled to -50 ° C or lower. Then 1.5
4 ml (6 mmol) of methyl lithium diluted with M diethyl ether was rediluted to 10 ml of diethyl ether and diluted for 15 minutes. After completion of the feed, the temperature was raised to −10 ° C. over 1 hour, and the reaction was performed while further rising 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 matter by filtration, the solvent was distilled off until the supernatant solution became about 10 ml, and the mixture was left in a freezer overnight.
White crystals were obtained. The crystals were separated, washed with a small amount of pentane, and then dried. As a result, 0.65 g of dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl was obtained.

Polymerization of Propylene To a fully dehydrated and deoxygenated toluene 5 was added to a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirring and temperature control device, which was sufficiently replaced with propylene gas.
00 ml, the same components as used in Example-1 (C
-1) to 2 mmol and trimethylaluminum to 3
6.0 mg, then 0.84 mg (2 μmol) of the dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl obtained above was introduced, 7
Polymerization was carried out at 0 ° C. for 7 kg / cm ² G for 2 hours. After completion of the polymerization, the slurry was extracted into 3 liters of methanol to sufficiently precipitate the polymer, which was then filtered and dried.
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> Polymerization of propylene was carried out under the same conditions as in Example-6 except that trimethylaluminum was not used in Example-6. The results are shown in Table 2. <Example-7> Production of component (C) In producing the component (C) of Example-1, instead of 19.8 g of triisobutylaluminum, 9.9 g of triisobutylaluminum and 3.6 g of trimethylaluminum. Component (C) was produced in the same manner as in Example 1 except that the reaction was carried out by mixing and diluting with 100 ml of toluene. As a result, 12.2 g of a liquid compound (C-3) was obtained.

Polymerization of Propylene Polymerization of propylene was carried out under the same conditions as in Example 6 except that 2 mmol of the component (C-3) obtained above was used. The results are shown in Table 2. <Examples-8 and 9, Comparative Example-6> In the polymerization of propylene of Example-7, instead of 36.0 mg of trimethylaluminum, 34.
3 mg, 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. The results are shown in Table 2. <Example-10> Production of component (A) Synthesis of dimethylsilylene (tetramethylcyclopentadienyl) tert-butylaminotitanium dichloride In a 300 ml flask which was sufficiently replaced with nitrogen,
Dehydrated and degassed tetrahydrofuran (THF) 100
Add milliliters, and use this (Kanto Chemical Co., Ltd.
-Butylamido) (tetramethylcyclopentadienyl) dimethylsilane 2.52 g (10 mmol) was dissolved. Then, after cooling this to −50 ° C. or lower,
13.4 ml (20 mmol) of methyllithium diluted with 1.5 M of diethyl ether was introduced over 10 minutes. Then, the temperature was raised to room temperature over 1 hour, and the reaction was performed at room temperature for 6 hours. After completion of the reaction, the solvent was distilled off, and the residue was washed with THF several times to obtain 2.16 g of dilithium (tert-butylamide) (tetramethylcyclopentadienyl) dimethylsilane.

Then, 100 ml of dehydrated and deoxygenated diethyl ether and 0.38 of titanium tetrachloride were placed in a 300 ml flask with sufficient nitrogen substitution.
Grams (2 mmol) were mixed below -50 ° C. Then, 2 mmol (0.53 g) of the dilithium (tert-butylamido) (tetramethylcyclopentadienyl) dimethylsilane obtained above was diluted with 10 ml of tetrahydrofuran, and the temperature was -50 ° C or lower. Was added dropwise over 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 one day. After the reaction,
After distilling off the solvent, 50 ml of toluene was added and lithium chloride was removed by filtration. Then, toluene was distilled off, 30 ml of n-pentane was added and dissolved, and the mixture was stored in a refrigerator for one day and night. As a result, 0.25 g of yellow crystals of the objective dimethylsilylene (tetramethylcyclopentadienyl) tert-butyl were obtained. Amidotitanium 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 min, 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 greatly improved, expensive alumoxane compounds are not required, and it is not necessary to use an aromatic hydrocarbon solvent which is an industrial limitation. Is as described above in the section "Summary of Invention".

[Brief description of drawings]

FIG. 1 is a ²⁷ Al-NMR diagram of bis (diisobutylaluminooxy) 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 Toso Akzo Co., Ltd.) used in Comparative Example-4.

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

FIG. 5 is intended to help an understanding of the technical content of the present invention regarding a Ziegler catalyst.

Claims (2)

[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 the catalyst. Component (A): Group IVB to VIB transition metal compound having at least one conjugated five-membered ring ligand, Component (B): Organoaluminum compound, Component (C): Compound having the following structure. [Chemical 1] (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ² is hydrogen, halogen, siloxy group, lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and 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 the catalyst. Component (A): Group IVB to VIB transition metal compound having at least one conjugated five-membered ring ligand, component (B): organoaluminum compound, component (C): the following component (i) and Reaction product of component (ii). Component (i): (However, R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms.) Component (ii): an organoaluminum compound.