JP3117246B2 - Olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for polymerizing olefins.

[0002]

2. Description of the Related Art Transition metal compounds having cyclopentadienyl group, indenyl group, fluorenyl group, or derivatives thereof as ligands, so-called metallocene compounds, are used together with a cocatalyst such as aluminoxane to polymerize an α-olefin. It is known that by doing so, a poly-α-olefin can be produced.

JP-A-58-19309 discloses that (cyclopentadienyl) ₂ MeRHal (where R is cyclopentadienyl, C ₁ -C ₆ alkyl and halogen, and Me is a transition metal. Yes, Ha
wherein l is a halogen), and a method of polymerizing or copolymerizing ethylene and / or an α-olefin in the presence of a catalyst comprising a transition metal compound represented by the formula: JP-A-60-35008 describes that a poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst comprising at least two kinds of metallocene compounds and an aluminoxane. JP-A-61-130314 describes a method for producing a polyolefin using a catalyst comprising a sterically fixed zircon chelate compound and an aluminoxane. The publication also discloses a method for producing a polyolefin having a high isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Are listed. JP-A-64-66
No. 124 discloses a transition metal compound having a cyclopentadienyl compound cross-linked with silicon as a ligand and a catalyst for producing a stereoregular olefin polymer containing aluminoxane as an active ingredient.

Japanese Patent Application Laid-Open No. 2-41303 discloses that the following formula R ″ (CpR _n ) (CpR ′ _m ) MeQ _k (where each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring) Each R _n is the same or different and is a hydrocarbyl residue having 1 to 20 carbon atoms; each R ′ _m is the same or different and is a hydrocarbyl residue having 1 to 20 carbon atoms; Yes; R "is a structural bridge between Cp rings that provides steric stiffness to the catalyst; Me is 4b, 5b,
Or a metal of Group 6b; each Q is a hydrocarbyl residue having 1 to 20 carbon atoms or halogen; 0 ≦ k ≦
3: 0 ≦ n ≦ 4 and 1 ≦ m ≦ 4; and R ′ _m is selected such that (CpR ′ _m ) is selected to be sterically different from (CpR _n ) Metallocene catalyst used to produce syndiotactic polyolefin. It is described that a poly-α-olefin having good syndiotacticity can be produced by using a catalyst containing as one component. Further, the publication discloses that a syndiotactic poly-α having a wide molecular weight distribution is obtained by using two or more of the above metallocene compounds.
It states that olefins can be produced.

[0005] JP-A-2-274703 discloses a compound represented by the following formula:

[0006]

Embedded image [Wherein, M ¹ is titanium, zirconium, vanadium, niobium or tantalum, and R ¹ and R ² may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom
Alkoxy group having 10 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, carbon atom Means an alkylaryl group having 7 to 40 atoms or an arylalkenyl group having 8 to 40 carbon atoms, R ³ and R ⁴ are different, and a central atom M
R ⁵ represents a mono- or polynuclear hydrocarbon group capable of forming a sandwich structure together with ¹

[0007]

Embedded image= BR⁶, = AlR⁶, -Ge-, -Sn-, -O-,
-S-, = SO, = SO, = NR⁶, = CO, = PR⁶
Or = P (O) R⁶, Where R⁶, R ⁷And
And R⁸May be the same or different, and
, A halogen atom, an alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, number of carbon atoms
6 to 10 fluoroaryl groups, 6 to 20 carbon atoms
Aryl group, alkoxy group having 1 to 10 carbon atoms, carbon
An alkenyl group having 2 to 10 atoms and 7 to 40 carbon atoms
Arylalkyl group, aryla having 8 to 40 carbon atoms
Lucenyl group or alkyl aryl having 7 to 40 carbon atoms
Or R⁶And R⁷Or R⁶You
And R⁸Are each formed with their attached atoms
To form a ring, and M^TwoIs silicon, germanium or
Is tin. The transition metal component represented by
Polymerization of olefins in the presence of a catalyst consisting of
And high molecular weight syndiotactic polyolefin
Are described.

[0008] JP-A-2-274704 describes a method for producing a high-molecular-weight syndiotactic polyolefin using the same hafnium compound. However, in a catalyst system using these aluminoxanes, it was necessary to use a large amount of expensive aluminoxanes in order to exhibit high catalytic activity.

On the other hand, so-called Kaminsky as described above
The active species of the type catalyst is [Cp '_TwoMR) ⁺(Where Cp '=
Clopentadienyl derivative, M = Ti, Zr, Hf, R
= Alkyl) as a transition metal cation
It has been suggested that aluminoxanes have been
Some catalyst systems have not been reported. Taube et al., J.
 Organometall. Chem.,347, C9 (1988) [Cp_TwoT
iMe (THF)]⁺[BPh_Four]^-(Me = methyl
Group, Ph = phenyl group)
Succeeded in len polymerization. Jordan et al., J. Am. Chem. S.
oc.,109, 4111 (1987), [Cp_TwoZrR (L)]⁺
(R = methyl group, benzyl group, L = Lewis base)
That a simple zirconium complex polymerizes ethylene
I have. Japanese Unexamined Patent Publication No. Hei 1-501950, Japanese Unexamined Patent Publication No. Hei 1-50
No. 2036 discloses cyclopentadienyl metal compounds and
And stabilize cyclopentadienyl metal cations
Using a catalyst consisting of an ionic compound
A method for polymerizing fins is described. Zambelli et al.
Macromolecules,twenty two, 2186 (1989)
Zirconium compounds having tadiene derivatives as ligands
And trimethyl aluminum and fluorodimethyl aluminum
Isotactic with a catalyst combined with
It reports that polypropylene can be produced. Ma
In order to reduce the amount of aluminoxane used,
Attempts have also been made to use a luminium compound in combination. JP
Japanese Unexamined Patent Publication No. 22223/1990 discloses a specific hafnium compound.
From aluminoxane and organoaluminum compounds
A method for polymerizing an olefin using a catalyst is disclosed.
ing.

[0010]

The Kaminsky catalyst system uses a large amount of expensive aluminoxane. Therefore, it is desired to develop a catalyst system in which the amount of aluminoxane used is reduced or a catalyst system which does not use aluminoxane. Several such catalyst systems have been proposed. However, there is a problem that an ionic compound which is difficult to synthesize must be used in order to obtain high activity with a catalyst system not using aluminoxane as described above.

[0011]

Means for Solving the Problems In order to solve the above problems, the present inventors have intensively studied a method of polymerizing an olefin without using an aluminoxane. It has been found that the above object can be achieved by using one component, and the present invention has been completed. That is, the present invention provides (A) a tetravalent zirconium having at least one cyclopentadienyl group, an indenyl group, a fluorenyl group, or a bridged or non-bridged ligand composed of a derivative thereof.
And a transition metal compound selected from the group consisting of titanium, hafnium, and a compound of (B) an organoaluminum compound and (C) a manganese halide compound. In the present invention, tetravalent zirconium, titanium and hafnium having at least one cyclopentadienyl group, an indenyl group, a fluorenyl group, or a cross-linked or non-cross-linked ligand thereof, which is used as the component (A), is used . Compound
The transition metal compound selected from the compounds is a known compound called a so-called metallocene compound. Specific examples include the following compounds.

Examples of the transition metal compound having a non-bridging ligand include cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, and bis (pentamethylcyclopentadiyl). (Enyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, and transition metal compounds having a bridging ligand include ethylenebis (1-indenyl) zirconium dichloride, ethylenebis (4,5, 6,7-tetrahydro1-
(Indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene In addition to cyclopentadienyl) (9-fluorenyl) zirconium dichloride, similar hafnium compounds, and the like, for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, and JP-A-3-21607. -1069
Transition metal compounds as described in JP-A-07-07, etc. can be exemplified.

[0013] Organic aluminum compounds used as component (B) in the present invention have the general formula _{^{R 1 j Al (OR 2)}} k H l X m ( wherein R ^1, R ² is up to 20 carbon atoms A hydrocarbon group, R ¹ and R ² may be the same or different, X is a halogen atom, O is an oxygen atom, H is a hydrogen atom, j is an integer of 1 to 3, k, l, and m are integers from 0 to 2 and j + k + 1 + m = 3), or a mixture thereof. Specifically, for example, trimethyl aluminum,
Examples thereof include triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, and diisobutylaluminum hydride. Among them, triethylaluminum and triisobutylaluminum are preferably used. The use ratio of the organoaluminum compound of the component (B) to the transition metal compound used as the component (A) is 0.1 to 10,000 mole times, preferably 1 to 10 moles.
It is 00 mole times.

The manganese halide compound used as the component (C) in the present invention includes known manganese halide anhydrides. Specifically, Mn
F ₂ , MnF _3, MnCl ₂ , MnCl ₄ , MnBr ₂ ,
MnI _{2 and the} like can be mentioned. These manganese halide compounds can be used as they are, but they can also be used after being ground using a known method such as grinding using a vibration mill. At that time,
The transition metal compound of the component (A) and / or the organometallic compound of the component (B) may coexist and may be brought into contact with each other by co-milling. The use ratio of the manganese halide compound of the component (C) to the transition metal compound used as the component (A) is 1 to 1,000,000 mole times, preferably 1 to 100000 mole times.

The polymerization method and the polymerization conditions carried out in the method of the present invention are not particularly limited, and known methods carried out in the polymerization of olefins are used, and a solvent polymerization method using an inert hydrocarbon medium or a substantially insoluble solvent is used. A bulk polymerization method or a gas phase polymerization method in which no active hydrocarbon medium is present can be used, and the polymerization is generally performed at a polymerization temperature of -100 to 200 ° C and a polymerization pressure of normal pressure to 100 kg / cm ² . Preferably, it is -50 to 100 ° C and normal pressure to 50 kg / cm ² .

The hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention includes, for example, benzene in addition to saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane. And aromatic hydrocarbons such as toluene and xylene. Examples of the olefin used in the polymerization include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. And α-olefins having 3 to 25 carbon atoms, and ethylene. In the present invention, it can be used not only for homopolymerization of olefins but also for producing copolymers of ethylene or α-olefins having about 2 to 25 carbon atoms such as propylene and ethylene or propylene and 1-butene.

[0017]

The present invention will be specifically described below with reference to examples. Example 1 Anhydrous manganese chloride (MnCl ₂ ) finely ground using a mortar in a 1.5-liter autoclave sufficiently purged with nitrogen.
1 g, triethylaluminum 0.3 g and JP-A-2
20 mg of isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride synthesized by the method described in JP-A-41303 was charged. Next, 0.75 l of liquid propylene was added, and polymerization was carried out at 40 ° C. for 1 hour. After the polymerization was stopped by adding a small amount of methanol into the system, propylene was purged and methanol
After washing with hydrochloric acid and drying, 5.6 g of syndiotactic polypropylene powder was obtained. Powder 1
Intrinsic viscosity ([η]) measured with 35 ° C tetralin solution
Was 0.55 dl / g, and the syndiotactic pentad fraction (rrrr) measured by ¹³ C-NMR was 0.85.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that triethylaluminum was not used, but no polymer was obtained.

Example 2 Instead of isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, ethylene bis (1-indenyl) synthesized as a transition metal compound component by the method described in JP-A-61-130314. ) As a result of performing polymerization in the same manner as in Example 1 except that 20 mg of zirconium dichloride was used, 3.8 g was obtained.
Of isotactic polypropylene powder was obtained. [Η] of the powder was 0.21 dl / g, and the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.72.

[Effect of the Invention] By performing the method of the present invention, a polyolefin can be produced without using an aluminoxane, which is extremely valuable industrially.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tetsunosuke Shiomura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Naoya Koide (56) References A) JP-A-59-197409 (JP, A) JP-A-2-173104 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] (A) a tetravalent having a bridged or non-bridged ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof;
Of zirconium, titanium and hafnium compounds
A method for polymerizing olefins, comprising polymerizing olefins in the presence of a catalyst comprising: (B) an organoaluminum compound (C) a manganese halide compound;