JP3144851B2 - Olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for the polymerization of olefins,
More particularly, it relates to a polymerization catalyst for 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, halogen, Me is a transition metal, and 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. Has been described. 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. JP-A-2-41303 discloses the following formula R ″ (CpR _n ) (CpR ′ _m ) MeQ _k (where each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; _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; R "is a structural bridge between the Cp rings that provides steric rigidity to the catalyst; Me is 4b, 5 of the Periodic Table of the Elements.
b is a metal of group b or 6b; each Q is a hydrocarbyl residue having 1 to 20 carbon atoms or halogen;
k ≦ 3: 0 ≦ n ≦ 4 and 1 ≦ m ≦ 4; and R ′
_m is selected such that (CpR ′ _m ) is sterically different from (CpR _n ), wherein the metallocene catalyst is used to produce a syndiotactic polyolefin. It is described that a poly-α-olefin having good syndiotacticity can be produced by using a catalyst containing as one component. The publication also discloses that syndiotactic poly-α-olefins having a wide molecular weight distribution can be produced by using two or more metallocene compounds. JP-A-2-274703 discloses a compound represented by the following formula (Chemical Formula 1).

[0003]

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

[0004]

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
Tin. ] The transition metal component represented by
Polymerizing olefins in the presence of a sun catalyst.
To produce high molecular weight syndiotactic polyolefin
A method of manufacture is described. Also, Japanese Patent Application Laid-Open No. 2-27
No. 4704 discloses the use of a similar hafnium compound.
Produce high molecular weight syndiotactic polyolefin
Methods are described. However, these
The catalyst system using luminoxane has high catalytic activity.
Use large amounts of expensive aluminoxanes to showcase
Needed.

On the other hand, the active species of the above-mentioned Kaminski type catalyst is [Cp ' ₂ MR] ⁺ (where Cp' = cyclopentadienyl derivative, M = Ti, Zr, Hf, R
= Alkyl), several catalyst systems not using aluminoxanes as cocatalysts have been reported.

Taube et al., J. Organometall. Chem., 34
7 , C9 (1988) shows [Cp ₂ TiMe (THF)] ⁺ [B
Ph _4] ^- (Me = methyl, Ph = phenyl group) with a compound represented by have successfully ethylene polymerization. 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. Tokiohei 1-5019
No. 50 and Japanese Patent Application Laid-Open No. 1-502036 disclose a method of polymerizing an olefin using a catalyst comprising a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. Has been described. Zambelli et al., Macromolecules, 22 , 21
86 (1989) reported that isotactic polypropylene can be produced by using a catalyst obtained by combining trimethylaluminum and fluorodimethylaluminum with a zirconium compound having a cyclopentadiene derivative as a ligand. JP-A-3-179005 discloses a metallocene catalyst comprising a) a neutral metallocene compound, b) an aluminum alkyl, and c) a Lewis acid. As an example, isopropylidene (cyclopentadienylfluorenyl) zirconium is disclosed. A method 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), reports that isotactic polypropylene can be produced by a catalyst comprising ethylenebis (tetrahydroindenyl) zirconium dichloride, trialkylaluminum, and magnesium chloride or alumina.

[0007]

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. Further, in a catalyst system using a solid acid such as magnesium chloride or alumina, according to the knowledge of the present inventors, in order to obtain sufficient catalytic activity, a solid acid is prepared by a special method, 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 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 relates to (A) titanium or zirconium having at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a crosslinked or non-bridged ligand comprising a derivative thereof.
Um and a transition metal compound selected from the compounds of hafnium (B) an organic aluminum compound (C) a magnesium halide (D) formula MX _n (M is a typical element of the Periodic Table Group 3b, X is a halogen atom. (n is an integer of 1 to 3) is an olefin polymerization method characterized by polymerizing an olefin in the presence of a catalyst comprising a compound represented by the following formula:

In the present invention, titanium or zirconium having at least one cyclopentadienyl group, indenyl group, fluorenyl group or a derivative thereof having a crosslinked or non-bridged ligand used as the component (A).
And a transition metal compound selected from hafnium compounds are known compounds called so-called metallocene compounds. More specifically, for example, the following known compounds can be mentioned. Examples of the transition metal compound having a non-bridging ligand include cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, and bis (pentamethylcyclopentadienyl) zirconium. Examples of dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, and 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 De, isopropylidene (cyclopentadienyl) (9-Furuorenioru) zirconium dichloride, diphenylmethylene (cyclopentadienyl) such as (9-Furuorenioru) zirconium dichloride and the like. Other than similar hafnium compounds and the like, for example, JP-A-3-9913,
JP-A-2-131488, JP-A-3-21607
And transition metal compounds described in JP-A-3-106907.

[0010] 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). Specific examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum hydride and the like. 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 10000 mole times, preferably 1 to 1000 mole times. Examples of the magnesium halide used as the component (C) in the present invention include magnesium chloride and magnesium bromide. The component (D) has the general formula MX ₃
(M is a typical element of Group 3b of the periodic table, X represents a halogen atom, 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, as one component of the catalyst, the general formula MX _n (M, X and n are as described above)
Wherein the compound represented by the general formula MX is used.
compounds represented by _n is can be used as it is a fine powder as a component of the catalyst, particularly preferably used those treated with the compound represented magnesium halide with the general formula MX _n. Examples of the treatment method include a method in which both components are brought into contact in an organic solvent that does not react with both components, and a method in which both components are brought into contact using a crushing equipment such as a vibration mill. Preferred examples of the solvent used when contacting in an organic solvent include pentane, hexane, heptane, aliphatic hydrocarbons such as decane, benzene, toluene, xylene, and aromatic hydrocarbons such as tetralin, Examples thereof include halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and trichloroethane. The temperature for contacting both components is -10
The temperature is from 0 ° C to 500 ° C, preferably from -50 ° C to 300 ° C. The use ratio of the component (C) 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 the component (D) to the component (C) is 10 weight pp.
m to 1 part by weight, preferably 0.01 to 0.3 part by weight.

The polymerization method and the polymerization conditions carried out by 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 inert polymerization method 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, saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, as well as benzene. 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. Further, in the present invention, it can also be used for known polymerizations such as those performed using a metallocene catalyst, such as copolymerization of olefins with dienes or copolymerization of olefins with cyclic olefins.

[0015]

The present invention will be specifically described below with reference to examples. Example 1 Method for treating catalyst component (C) with (D) A 300 ml glass flask was charged with anhydrous magnesium chloride 5.0 g, anhydrous aluminum chloride 1.0 g and purified toluene 100 ml, and stirred for 3 hours in nitrogen under stirring. Reflux was performed. The supernatant was removed by decantation at 100 ° C., washed three times with toluene, and 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)
The following components were used as components. Polymerization In a 1.5-liter autoclave sufficiently purged 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 synthesis 0.8 g of the catalyst components (C) and (D) thus obtained were charged. Next, 0.75 l of liquid propylene was added, and polymerization was carried out at 40 ° C. for 1 hour. After terminating the polymerization by adding a small amount of methanol into the system, propylene was purged, washed with methanol / hydrochloric acid, and dried to obtain 10.6 g of syndiotactic polypropylene powder. 135 ° C of powder
The intrinsic viscosity ([η]) measured with a tetralin solution of 0.1 was 0.1.
The syndiotactic pentad fraction (rrrr) measured by 82 dl / g and 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 a method described in JP-A-61-130314. ) As a result of conducting polymerization in the same manner as in Example 1 except that 10 mg of zirconium dichloride was used, 3.8 g was obtained.
Of isotactic polypropylene powder was obtained. [Η] of the powder was 0.27 dl / g, and the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR was 0.72.

Comparative Example 2 Anhydrous magnesium chloride 0.8 without using the catalyst component (D)
Polymerization was carried out 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.

Embodiment 3Method for treating 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
And stirred for 3 days at room temperature in nitrogen.
Was. The supernatant is removed by decantation, and
After washing with toluene three times, the resultant is dried under reduced pressure.
As a result, 5.1 g of a white powder was obtained. Obtained in this way
The following polymerization was performed using white powder as catalyst components (C) and (D).
Used for polymerization In a 1.5-liter autoclave sufficiently purged with nitrogen,
Lopylidene (cyclopentadienyl) (9-fluorenyl)
G) zirconium dichloride 10 mg, triethyl al
0.5 g of minium and the catalyst component (C) synthesized above
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 methanol
After stopping the polymerization by adding
Purge pyrene, wash with methanol / hydrochloric acid, and dry
Of 1.1 g of syndiotactic polypropylene
I got powder. 135 ° C tetralin solution of powder
The intrinsic viscosity ([η]) measured with the liquid is 0.82 dl / g,
¹³Syndiotactic pentad measured by C-NMR
The fraction (rrrr) was 0.83.

[0020]

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

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsunosuke Shiomura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Shoko Mitani (56) References JP-A-3-179005 (JP, A JP-A-4-211405 (JP, A) JP-A-63-168408 (JP, A) JP-A-63-89513 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (1)

(57) [Claims] 1. A (A) at least one cyclopentadienyl group, indenyl group, Chita having fluorenyl group or a bridged or non-bridging ligands consisting of derivatives,
Emissions, zirconium and compounds from selected <br/> transition metal compound of hafnium (B) an organic aluminum compound (C) a magnesium halide (D) formula MX _n (M is a typical element of the Periodic Table Group 3b, X Is a halogen atom, and n is an integer of 1 to 3).