JPH0597923A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin without using expensive aluminoxane by using a catalyst composed of a metallocene compound, an organic Al compound, a magnesium halide and a specific compound. CONSTITUTION:An olefin is polymerized preferably at -50 to +100 deg.C under normal pressure to 50kg/cm<2> in the presence of a catalyst composed of (A) a transition metal compound of group 4-6 of the periodic table, having (non) crosslinked ligand and composed of cyclopentadienyl, indenyl, fluorenyl or their derivative (preferably a group 4 metal metallocene compound such as cyclopentadienylzirconium trichloride), (B) an organic Al compound (preferably triethylaluminum), (C) a magnesium halide (e.g. magnesium chloride) and (D) a compound of formula MXn (M is typical element of group 3b of the periodic table; X is halogen; (n) is 1-3) (e.g. boron trichloride).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a method for polymerizing olefins,
More specifically, it relates to an olefin polymerization catalyst.

[0002]

A transition metal compound having a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand, a so-called metallocene compound, is used together with a cocatalyst such as an aluminoxane to polymerize an α-olefin. It is known that a poly-α-olefin can be produced by JP-A-58-19309 discloses (Cyclopentadienyl) ₂ MeRHal (wherein R is cyclopentadienyl, C ₁ -C ₆ alkyl, halogen, Me is a transition metal, and Ha is Ha.
1 is a halogen) and a method of polymerizing or copolymerizing ethylene and / or α-olefin in the presence of a catalyst composed of a transition metal compound represented by the formula (1) and aluminoxane. Japanese Unexamined Patent Publication (Kokai) No. 60-35008 describes that a poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst composed of at least two kinds of metallocene compounds and aluminoxane. Japanese Patent Laid-Open No. 61-130314 describes a method for producing a polyolefin using a catalyst composed of a sterically fixed zircon chelate compound and an aluminoxane. Further, the publication discloses a method for producing a polyolefin having a high degree of isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Have been described. JP-A-64-66
Japanese Unexamined Patent Publication No. 124 discloses a catalyst for producing a stereoregular olefin polymer containing a transition metal compound having a silicon-crosslinked cyclopentadienyl compound as a ligand and an aluminoxane as an active ingredient. JP-A-2-41303, there by the following formula _{R "(Cp R n) (} CpR 'm) MeQ k ( where each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R _n may be the same or different, from 1 to 20 a hydrocarbyl residue having a carbon atom; may optionally each R _'m mother same or different, is a hydrocarbyl residue having 1 to 20 carbon atoms; R "is the structural bridge between the Cp rings that gives the catalyst steric rigidity; Me is 4b, 5 of the Periodic Table of the Elements.
a metal of group b, or 6b; each Q is a hydrocarbyl residue having from 1 to 20 carbon atoms or a halogen; 0 ≦
k ≦ 3: 0 ≦ n ≦ 4: and 1 ≦ m ≦ 4; and R ′
_m is (CpR _'m) is (CpR _n) and sterically different and is selected as the metallocene catalyst used to produce the syndiotactic polyolefin is denoted by. It is described that a poly-α-olefin having a good syndiotacticity can be produced by using a catalyst containing 1 component as a component. Further, the same publication describes that the syndiotactic poly-α-olefin having a wide molecular weight distribution can be produced by using two or more kinds of the above metallocene compounds. Japanese Unexamined Patent Publication No. 2-274703 discloses the following formula (Formula 1).

[0003]

[Chemical 1] [In the formula, M ¹ is titanium, zirconium, vanadium, niobium or tantalum, R ¹ and R ² may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom
An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a carbon atom. A C 7-40 alkylaryl group or a C 8-40 arylalkenyl group, wherein R ³ and R ⁴ are different and the central atom M
¹ means a mononuclear- or polynuclear hydrocarbon group capable of forming a sandwich structure together with ^1, and R ⁵ is

[0004]

[Chemical 2]= BR⁶, = AlR⁶, -Ge-, -Sn-, -O-,
-S-, = SO, = SO, = NR⁶, = CO, = PR⁶
Or = P (O) R⁶Means R in that case⁶, R ⁷And
And R⁸Can be the same or different from each other,
Child, halogen atom, alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, number of carbon atoms
6-10 fluoroaryl group, 6-20 carbon atoms
Aryl group, alkoxy group having 1 to 10 carbon atoms, carbon
Alkenyl group having 2 to 10 atoms, having 7 to 40 carbon atoms
Arylalkyl group, an aryl group having 8 to 40 carbon atoms
Lucenyl group or alkylaryl having 7 to 40 carbon atoms
Means a radical or R⁶And R⁷Or R⁶Oh
And R⁸Are each made up of the atoms that they bond to
Form a ring, and M²Is silicon, germanium or
It is tin. ] A transition metal component represented by
Polymerizing olefins in the presence of a catalyst consisting of Sun
High molecular weight syndiotactic polyolefin
A method of manufacturing is described. In addition, JP-A-2-27
In 4704, a similar hafnium compound is used.
Manufactures high molecular weight syndiotactic polyolefins
Method is described. However, these
A catalyst system using luminoxane exhibits high catalytic activity.
Use a large amount of expensive aluminoxane to reveal
There was a need.

On the other hand, the active species of the above-mentioned so-called Kaminsky type catalyst is [Cp ' ₂ MR] ⁺ (where Cp' = cyclopentadienyl derivative, M = Ti, Zr, Hf, R
= Alkyl), some catalyst systems that do not use aluminoxanes as co-catalysts have been reported since they were suggested to be transition metal cations.

Taube et al., J. Organometall. Chem., 34 .
7 , C9 (1988) [Cp ₂ TiMe (THF)] ⁺ [B
Ethylene polymerization was successful using a compound represented by Ph ₄ ] ^- (Me = methyl group, Ph = phenyl group). Jo
rdan et al. in J. Am. Chem. Soc., 109 , 4111 (1987),
It shows that a zirconium complex such as [Cp ₂ ZrR (L)] ⁺ (R = methyl group, benzyl group, L = Lewis base) polymerizes ethylene. Special table 1-5019
No. 50 and Japanese Patent Publication No. 1-502036 disclose a method of polymerizing an olefin using a catalyst composed of a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. Have been described. Zambelli et al., Macromolecules, 22 , 21,
86 (1989) reported that isotactic polypropylene can be produced by a catalyst in which a zirconium compound having a cyclopentadiene derivative as a ligand and trimethylaluminum and fluorodimethylaluminum are combined. JP-A-3-179005 discloses a metallocene catalyst comprising a) a neutral metallocene compound, b) aluminum alkyl, and c) Lewis acid, and isopropylidene (cyclopentadienylfluorenyl) zirconium is used as an example. A process for obtaining syndiotactic polypropylene using a catalyst consisting of dimethyl / triethylaluminum / magnesium chloride is described. Soga et al., Makromol. Chem., Rapid C
ommun. 12 , 367 (1991), it is reported that isotactic polypropylene can be produced with a catalyst composed of ethylenebis (tetrahydroindenyl) zirconium dichloride, trialkylaluminum, and magnesium chloride or alumina.

[0007]

Since the Kaminsky catalyst system uses a large amount of expensive aluminoxane, 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 that is difficult to synthesize must be used in order to obtain high activity in the catalyst system that does not use aluminoxane as described above. Further, in the case of a catalyst system using a solid acid such as magnesium chloride or alumina, according to the findings of the present inventors, in order to obtain a sufficient catalytic activity, the solid acid is prepared by a special method or the solid acid It was necessary to improve the surface area.

[0008]

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted extensive studies on a method for polymerizing an olefin without using an aluminoxane, and as a result, a known compound that is easily available is used as a cocatalyst. The inventors have found that the above-mentioned objects can be achieved by using one component, and have completed the present invention. That is, the present invention provides (A) a transition metal compound of Group 4 to 6 of the periodic table having a bridged or non-bridged ligand composed of at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof. ) Organoaluminum compound (C) Magnesium halide (D) General formula MX _n (M is a typical element of Group 3b of the Periodic Table, X is a halogen atom, and n is an integer of 1 to 3) Is a method for polymerizing olefins in the presence of a catalyst.

Periodic Tables 4 to 6 having at least one cyclopentadienyl group, indenyl group, fluorenyl group or a derivative thereof, which is used as the component (A) in the present invention, having a bridging or non-bridging ligand. Group transition metal compounds are known compounds called so-called metallocene compounds. Among them, metallocene compounds of Group 4 of the periodic table are preferably used. More specifically, the following known compounds can be given as examples. Examples of the transition metal compound having a non-bridging ligand are cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, and bis (pentamethylcyclopentadienyl) zirconium. Dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, transition metal compounds having a bridging ligand include ethylenebis (1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7) -Tetrahydro 1-
Indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenniol) zirconium dichloride, diphenylmethylene ( Cyclopentadienyl) (9-fluorenyl) zirconium dichloride and the like. In addition to the similar hafnium compounds and the like, for example, JP-A-3-9913 and JP-A-2-
Examples thereof include transition metal compounds described in JP-A-131488, JP-A-3-21607 and JP-A-3-106907.

The organoaluminum compound used as the component (B) in the present invention is represented by the general formula R ¹ _j Al (OR ² ) _k H _l X _m (wherein R ¹ and R ² have 1 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 from 1 to 3, k, l, and m are integers from 0 to 2, and can be represented by j + k + l + m = 3). Specific examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum hydride and the like. Among them, triethylaluminum and triisobutylaluminum are preferably used.

The proportion of the organoaluminum compound as the component (B) used with respect to the transition metal compound used as the component (A) is 0.1 to 10000 mol times, preferably 1 to 1000 mol times. Examples of the magnesium halide used as the component (C) used in the present invention include magnesium chloride and magnesium bromide. Component (D) has the general formula MX ₃
(M is a typical element of Group 3b of the periodic table, X is a halogen atom, and n is an integer of 1 to 3), and specifically, for example, boron trichloride, aluminum chloride, gallium chloride. , Indium chloride, thallium chloride, boron tribromide, aluminum bromide, gallium bromide, indium bromide, thallium bromide and the like.

A feature of the present invention is that one component of the catalyst has the general formula MX _n (M, X, n are as described above).
The compound represented by the general formula MX
_{As the} compound represented by _n , fine powder can be used as it is as one component of the catalyst, but particularly preferably, magnesium halide treated with the compound represented by the general formula MX _n can be used. Examples of the treatment method include a method of bringing both components into contact with each other in an organic solvent that does not react with both components, and a method of bringing both components into contact with each other using a pulverizing facility such as a vibration mill. Preferable examples of the solvent used when contacting in an organic solvent include pentane, hexane, heptane, and aliphatic hydrocarbons such as decane, benzene, toluene, xylene, and aromatic hydrocarbons such as tetralin, Mention may be made of halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and trichloroethane. The temperature for contacting both components is -10
It is 0 ° C to 500 ° C, preferably -50 ° C to 300 ° C. The ratio of the component (C) used to the transition metal compound used as the component (A) is 1 to 1,000,000 times by weight, preferably 1 to 100,000 times by weight. The amount of component (D) used with respect to component (C) is 10 weight pp.
m to 1 part by weight, preferably 0.01 to 0.3 part by weight.

There are no particular restrictions on the polymerization method and polymerization conditions used in the method of the present invention, and known methods used in the polymerization of olefins may be used. Solvent polymerization methods using an inert hydrocarbon medium, or substantially A bulk polymerization method or a gas phase polymerization method in which an active hydrocarbon medium does not exist can also be used, and it is general to carry out at a polymerization temperature of −100 to 200 ° C. and a polymerization pressure of atmospheric pressure to 100 kg / cm ² . The pressure is preferably −50 to 100 ° C. and atmospheric pressure to 50 kg / cm ² .

Examples of the hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, and benzene. Aromatic hydrocarbons such as, toluene, xylene, etc. can also be used. The olefin used in the polymerization includes propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene. And α-olefins having 3 to 25 carbon atoms, or 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, propylene and 1-butene. Further, in the present invention, it can also be used for known polymerizations that are carried out using a metallocene catalyst, for example, copolymerization of olefins and dienes, copolymerization of olefins and cyclic olefins, and the like.

[0015]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 Treatment of catalyst component (C) with (D) A 300 ml glass flask was charged with 5.0 g of anhydrous magnesium chloride, 1.0 g of anhydrous aluminum chloride and 100 ml of purified toluene, and the mixture was stirred in nitrogen for 3 hours. Reflux was performed. The supernatant liquid was removed by decantation at 100 ° C., washed with toluene three times, and then dried under reduced pressure to obtain 5.3 g of a yellow powder. The yellow powder thus obtained is used as catalyst components (C) and (D).
It was used as a component in the following polymerization. Polymerization In a 1.5 liter autoclave sufficiently substituted with nitrogen, 10 mg of isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride synthesized by the method described in JP-A-2-41303, 0.5 g of triethylaluminum and the above-mentioned synthesis. 0.8 g of the catalyst components (C) and (D) prepared above were 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 to the system, propylene was purged, washed with methanol / hydrochloric acid, and dried to obtain 10.6 g of syndiotactic polypropylene powder. 135 ℃ of powder
The intrinsic viscosity ([η]) measured with the tetralin solution of No.
82dl / g, ¹³ syndiotactic pentad fraction measured by C-NMR (rrrr) 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, ethylenebis (1-indenyl) synthesized as a transition metal compound component by the method described in JP-A-61-130314. ) Polymerization was carried out in the same manner as in Example 1 except that 10 mg of zirconium dichloride was used.
To obtain isotactic polypropylene powder. The powder [η] was 0.27 dl / g, and the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.72.

Comparative Example 2 0.8 g of anhydrous magnesium chloride was used without using the catalyst component (D).
Polymerization was performed in the same manner as in Example 1 except that g was used as it was. As a result, only 0.1 g of syndiotactic polypropylene powder was obtained.

Example 3Treatment method of catalyst component (C) with (D) Anhydrous magnesium chloride in a 300 ml glass flask
5.0 g, boron trichloride 1.0 g and purified toluene 1
Charge 00 ml and stir in nitrogen at room temperature for 3 days.
It was The supernatant is removed by decantation, and
After washing with toluene three times, it is dried under reduced pressure.
Thus, 5.1 g of white powder was obtained. Thus obtained
The following polymerization using white powder as catalyst components (C) and (D)
Used for. polymerization Into a 1.5 l autoclave that had been thoroughly replaced with nitrogen,
Ropylidene (cyclopentadienyl) (9-fluorenyl
Ru) Zirconium dichloride 10 mg, triethyl al
0.5 g of minium and the above-synthesized catalyst component (C)
0.8 g was charged. Next, 0.75 l of liquid propylene
Was added and polymerization was carried out at 40 ° C. for 1 hour. A small amount of methano
Is added to the system to stop the polymerization and then the
Pyrene is purged, washed with methanol and hydrochloric acid, and dried.
This gives 1.1 g of syndiotactic polypropylene.
Got powder. 135 ° C tetralin solution of powder
The intrinsic viscosity ([η]) measured with the liquid is 0.82 dl / g,
¹³Syndiotactic pentads measured by C-NMR
The fraction (rrrr) was 0.83.

[0020]

Industrial Applicability By carrying out the method of the present invention, a polyolefin can be produced without using an aluminoxane, which is extremely industrially valuable.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazumi Mizutani, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Tetsunosuke Shiomura 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Higashi Mitsui Pressure Chemical Co., Ltd.

Claims (1)

[Claims] 1. A transition metal compound of Group 4 to 6 of the periodic table having a bridged or non-bridged ligand comprising (A) at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof. B) organoaluminum compound (C) magnesium halide (D) compound represented by the general formula MX _n (M is a typical element of Group 3b of the periodic table, X is a halogen atom, and n is an integer of 1 to 3) An olefin polymerization method comprising polymerizing an olefin in the presence of a catalyst comprising