JPH0656929A - Solid catalyst for olefin polymerization - Google Patents

Abstract

(57) [Summary] [Structure] A solid in which one or more ligands of a transition metal compound of Group IV or V of the periodic table has a chemical bond with an inorganic compound or an organic polymer compound carrier, And / or a solid catalyst for olefin polymerization which is contact-treated with an organoaluminum compound. [Effect] Since the shape of the catalyst is good and the polymerization activity is high, deashing is not required. An olefin copolymer having a narrow composition and a narrow molecular weight distribution and excellent mechanical properties can be produced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solid catalyst for olefin polymerization.

[0002]

2. Description of the Related Art In recent years, Ti, Zr, Hf, V, etc., which are highly active as olefin polymerization catalysts and which can obtain olefin polymers having a narrow molecular weight distribution and a narrow composition distribution in copolymerization and excellent physical properties, etc. Metallocene-type homogeneous catalysts of transition metal compounds have been attracting attention.

However, the above-mentioned homogeneous catalyst has a problem that an organoaluminum oxy compound, particularly expensive methylalumoxane, is required as a co-catalyst at the time of olefin polymerization, in thousands to tens of thousands times the transition metal atom. Various improvement methods have been proposed so far. For example, JP-A 61-31404, JP-A 61-276805, JP-A 61-108610, and JP-A 61-29600.
No. 8, JP-A-63-501369, JP-A-1
-207303, Japanese Patent Publication No. 1-503715, Japanese Patent Publication No. 2-503687, and Japanese Patent Application Laid-Open No. 2-178080.
No. 5, JP-A-3-502210, and JP-A-3-23710 disclose that a transition metal compound is supported on a porous inorganic compound carrier, or an organoaluminum oxy compound and / or an organoaluminum compound is used. A catalyst system in which the amount of aluminum oxy compound used is reduced by carrying the catalyst is disclosed. However, even with these improved methods, it cannot be said that the polymerization activity is high enough to be industrially adopted.

Therefore, it is desired to develop a catalyst system having a high polymerization activity without using an organoaluminum oxy compound, or by using as little an organoaluminum oxy compound as possible.

[0005]

SUMMARY OF THE INVENTION The present invention provides one or more ligands of Group IV or V transition metal compounds of the periodic table,
The present invention relates to a solid catalyst for olefin polymerization, characterized in that the transition metal compound-supported solid chemically bonded to an inorganic compound carrier or an organic polymer compound carrier is subjected to a contact treatment with an organic aluminum oxy compound and / or an organic aluminum compound.

Conventionally, a solid catalyst in which a transition metal compound is physically adsorbed on the surface of an inorganic compound carrier or an organic polymer compound carrier is known. However, in the present invention,
Disclosed is a solid catalyst in which an inorganic compound carrier or an organic polymer compound carrier and a ligand of a transition metal compound are directly chemically bonded.

As the inorganic compound carrier in the present invention,
Inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonates and sulfates can also be used. Particularly preferred are inorganic oxides, silica, alumina,
Magnesia, titania, zirconia, calcia, etc. can be mentioned. These inorganic oxide carriers are preferably porous fine particles having an average particle diameter of 5 to 150 μm and a specific surface area of ² to 800 m ² / g. Moreover, it is preferable to use after heat-treating at 100-800 degreeC. Especially, 500-8
It is preferable to use silica or alumina heat-treated at 00 ° C.

The organic polymer compound carrier in the present invention is preferably one having an aromatic ring, a substituted aromatic ring or a functional group such as a hydroxy group, a carboxyl group, an ester group or a halogen atom in its side chain. As specific examples, those having a functional group obtained by chemically modifying a homopolymer or copolymer of α-olefin such as ethylene, propylene and butene-1, acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, etc. Examples thereof include homopolymers or copolymers thereof, and chemically modified products thereof. As the shape of these organic polymer compound carriers, spherical fine particles having an average particle diameter of 5 to 250 µ are preferable.

The transition metal in the group IV or V transition metal compound of the periodic table in the present invention includes Ti, Zr,
Hf and V are preferred. Examples of the ligand that forms a metal compound by coordinating to these transition metals and forming a chemical bond with the above-mentioned inorganic compound carrier or organic polymer compound carrier include cyclopentadienyl group, methyl, dimethyl, pentamethyl, etc. Cyclic unsaturated hydrocarbon groups such as alkyl-substituted cyclopentadienyl group, indenyl group, and fluorenyl group are preferable. In this case, the chemical bond between the carrier and the ligand is formed by the carbon atom of the cyclic unsaturated hydrocarbon group, or the carbon atom or oxygen atom of the substituent.

Further, one or more of the above-mentioned ligands are alkylene group, substituted alkylene group, silanylene group, substituted silanylene group, silaalkylene group, substituted silaalkylene group, oxasilanylene group, substituted oxasilanylene group, oxasilan. An alkylene group, a substituted oxasilaalkylene group,
It may be a ligand bonded to an aminosilyl group, a mono-substituted aminosilyl group, a phosphinosilyl group, a mono-substituted phosphinosilyl group, or a bridged ligand. Examples of the substituent of these ligands include a hydroxy group, a carboxyl group, an ester group and a halogen atom.
In the case of a silanylene group, a silaalkylene group, an oxasilanylene group, or an oxasilaalkylene group, an ether group is also suitable as a substituent. In this case, the chemical bond between the carrier and the ligand is a carbon atom such as an alkylene group, a silanylene group, a silaalkylene group, an oxasilanylene group, an oxasilalkylene group, a silyl group or a silicon atom, or a carbon atom of the substituent or It can be formed by an oxygen atom.

On the other hand, in the present invention, the transition metal compound is a ligand that forms a chemical bond with the surface of the above-mentioned inorganic compound carrier or organic polymer compound carrier, and the remaining ligands that do not form a chemical bond. May have. As these ligands, the same ligands that form the chemical bond described above can be adopted. Further, a hydrogen atom, a hydrocarbon group having 1 to 16 carbon atoms, an RO group (R represents a hydrocarbon group having 1 to 16 carbon atoms), a halogen atom and the like can be exemplified.

In the present invention, the method for producing the transition metal compound-supporting solid in which one or more of the ligands of the transition metal compound has a chemical bond with the surface of the inorganic compound carrier is, for example, the following (1) or (2). There is a method like. The following is
In particular, this is an example in which a ligand forms a chemical bond with an inorganic compound carrier by an oxygen atom.

(1) First, a metal salt is formed by a reaction between a surface hydroxyl group of an inorganic compound carrier and an organometallic compound of Groups I to III of the periodic table. Next, the metal salt is reacted with a ligand precursor of a transition metal compound having a halogen atom or an RO group (R represents a hydrocarbon group having 1 to 16 carbon atoms) to coordinate with the inorganic compound. Chemically bond the child. The ligand chemically bonded to the surface hydroxyl group of the above-mentioned inorganic compound carrier is again reacted with an organometallic compound of Group I to III of the periodic table to form a metal salt. Finally, the metal salt
It is reacted with a transition metal compound precursor having a halogen atom and / or an RO group (R represents a hydrocarbon group having 1 to 16 carbon atoms) and / or a hydrocarbon group. This precursor is preferably a transition metal compound having at least one halogen atom or RO group.

(2) First, the surface hydroxyl groups of the inorganic compound carrier are halogenated with hydrogen halide. Next, the halogenated inorganic compound carrier is reacted with a ligand precursor of a transition metal compound having an OH group in the presence of a base to chemically bond the inorganic compound carrier and the ligand. Furthermore, the above (1)
Similarly, the transition metal compound precursor is coordinated with the ligand chemically bonded to the surface hydroxyl group of the inorganic compound carrier.

It is desirable that the halide of an organometallic group I to III or hydrocarbyl oxydide produced in the above-mentioned manufacturing process be dissolved and flowed out with an ether solvent such as THF.

In the present invention, one or more of the ligands of the transition metal compound has a chemical bond with the surface of the organic polymer compound carrier, and a method for producing the transition metal compound-supported solid is as follows:
For example, the following method (3) or (4) may be mentioned.

(3) First, a metal salt is formed by reacting an organic polymer compound carrier having an aromatic ring such as a copolymer of divinylbenzene and styrene with an organometallic compound of Group I to III of the periodic table. To form. Then, the metal salt is reacted with a ligand precursor of a transition metal compound having a halogen atom or an RO group (R represents a hydrocarbon group having 1 to 16 carbon atoms) to give an organic polymer compound carrier. And chemically bond the ligand. The ligand chemically bonded to the organic polymer compound carrier is again reacted with the organometallic compound carrier of Group I to III of the periodic table to form a metal salt. Finally, the above metal salt is reacted with a halogen atom and / or a RO group (R represents a hydrocarbon group having 1 to 16 carbon atoms) and / or a transition metal compound precursor having a hydrocarbon group. This precursor is preferably a transition metal compound having at least one halogen atom or RO group.

(4) First, a metal salt is formed by a reaction between an organometallic compound of Groups I to III of the periodic table and a ligand precursor of a transition metal compound. Next, an organic polymer compound carrier having a substituent such as a hydroxy group, a carboxyl group, an ester group, or a halogen atom is reacted to chemically bond a ligand to the organic polymer compound carrier. Further, in the same manner as in the above (3), the transition metal compound precursor is coordinated with the ligand chemically bonded to the organic polymer compound carrier.

It is desirable that the organometallic halide of group I to III of the periodic table or the hydrocarbyl oxydide produced in the above-mentioned manufacturing process be dissolved and flown out with an ether solvent such as THF.

In the above-mentioned method for producing a transition metal compound-supported solid, the organometallic compound of Groups I to III of the Periodic Table is preferably an alkyl, aryl or alkyl halide such as Li, Na, Mg or Al. As the precursor of the transition metal compound, a tetrahalogenated compound, a tetraalkoxy compound, a trihalogenoalkoxy compound, a dihalogenodialkoxy compound, a trihalogenoalkylated compound, a dihalogenodialkylated compound of a transition metal of Group IV or V of the Periodic Table can be used. Can be mentioned. Examples of the ligand precursor of the transition metal compound include a halide, a hydrocarbyl oxydide or a hydroxide having the above ligand.

In the present invention, the solid catalyst for olefin polymerization of the present invention is obtained by subjecting the above-mentioned transition metal compound-supported solid to catalytic treatment with an organoaluminumoxy compound and / or an organoaluminum compound.

The organoaluminum oxy compound is a linear or cyclic polymer represented by the general formula (-Al (R) O-) _n , where R is a hydrocarbon group having 1 to 10 carbon atoms, A part of R may be substituted with a halogen atom and / or an RO group. n is the degree of polymerization and is 5 or more, preferably 10 or more.

As the method for producing the organoaluminum oxy compound, for example, an inorganic compound containing water of crystallization and an organoaluminum compound are prepared by reacting a water-containing inert hydrocarbon solvent with the organoaluminum compound. Examples thereof include a method of reacting or introducing a hydrous olefin gas into an inert hydrocarbon solvent containing an organoaluminum compound during olefin polymerization to simultaneously produce an organoaluminum oxy compound.

The organoaluminum compound means the general formula Al
R _m X _3-m (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen atom or a hydrogen atom, and m represents 0.
<M ≦ 3). Examples thereof include trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, alkenylaluminum, dialkylhydroaluminum and sesquialkylhydroaluminum.

In the present invention, the olefin can be polymerized by the following method using the above-mentioned solid catalyst for olefin polymerization. However, in the present invention, olefin polymerization also includes olefin polymerization and copolymerization between olefins. (1) The olefin is polymerized in the presence of the solid catalyst contact-treated with the organoaluminum oxy compound and / or the organoaluminum compound. (2) Olefin is polymerized in the presence of the above-mentioned organoaluminum oxy compound and / or the solid catalyst contact-treated with the organoaluminum compound and the organoaluminum oxy compound and / or the organoaluminum compound as a co-catalyst.

As the organoaluminum oxy compound and the organoaluminum compound as the cocatalyst used in the above-mentioned olefin polymerization or copolymerization, the organoaluminum oxy compound and the organoaluminum compound using the above-mentioned solid catalyst for the contact treatment should be used. You can

The olefin polymerization in the present invention can be applied to any of the stirring type or fluidized bed type gas phase method, the slurry method and the solution method. In particular, the present invention which uses a solid catalyst in which the shape of the catalyst is easy to control can be preferably used in the gas phase method.

The slurry method or gas phase polymerization method in the present invention is
Usually, it can be carried out under conditions of 5 to 100 ° C. and 20 to 300 minutes, the atomic ratio of the transition metal in the solid catalyst to Al is 10 to 300, and the polymerization pressure is normal pressure to 130 kg / cm ² .
The high-temperature high-pressure polymerization method in the present invention is usually 100 to 300 ° C.
It can be carried out for 5 to 600 seconds under a polymerization pressure condition where the atomic ratio of the transition metal to aluminum in the solid catalyst is 5 to 200 and 130 kg / cm ² or more.

Further, the polymerization activity is improved, the shape of the solid catalyst of the produced polymer is maintained, the catalyst is easily introduced into the polymerization reaction vessel, the catalyst is prevented from adhering to the polymerization reaction vessel, and the fluidity in the gas phase reaction vessel is improved. For this purpose, an olefin preliminarily polymerized according to the above-mentioned various polymerization methods can be used as a catalyst in the main polymerization. The prepolymerization is usually carried out in a slurry method in an inert hydrocarbon solvent, for example, in the range of 5 to 5.
It can be carried out at 80 ° C. for 5 to 60 minutes under the condition that the atomic ratio of the transition metal in the solid catalyst to Al is 5 to 300 and 1 to 100 g of the olefin polymer is obtained per 1 mg of the transition metal of the solid catalyst.

Specific examples of the olefin polymerized by using the solid catalyst of the present invention include aliphatic monoolefins such as ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, and cyclopentene. ,
Examples thereof include cyclic monoolefins such as cyclohexene and norbornene. Further, in the above-mentioned olefin polymerization and copolymerization, dicyclopentadiene,
Non-conjugated linear or cyclic diolefins such as 5-ethylidene-2-norbornene, vinylcyclohexene, or 1.5-hexadiene can be copolymerized.

[0031]

When an olefin polymer is produced using the solid catalyst of the present invention, the shape of the catalyst is good, the operation of the catalyst is easy, and there is no polymer adhesion or clogging in the reaction vessel.
Since the polymerization activity is high, there are few transition metal and aluminum components in the produced polymer, and therefore deashing is not necessary. Further, in olefin copolymerization, a copolymer having a narrow composition and a narrow molecular weight distribution and excellent mechanical properties can be produced.

[0032]

EXAMPLES In the examples, “polymerization activity” is the polymer yield (kg) per 1 g of transition metal of the solid catalyst used in the polymerization reaction. "MI" means ASTMD-12
230 ° C. under a load of 2.16 kg / cm ² according to No. 38.
It is the melting index of the polymer measured in. The molecular weight distribution was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained from GPC using polystyrene as a standard substance. The content of transition metal in the solid catalyst was measured by a colorimetric method, and the content of comonomer in the copolymer was measured by H-NMR. The composition distribution of the copolymer was evaluated by the relationship between the density of the copolymer and the comonomer content. That is, at a constant comonomer content, the smaller the density, the narrower the composition distribution.

Example 1 [Preparation of solid catalyst] Silica (TG-20402 manufactured by Fuji Devison Chemical Co., Ltd. average particle diameter 40 μ) was mixed with 2 in a nitrogen stream.
2 hours at 00 ℃, 4 hours at 600 ℃, 800 ℃
It was baked for 2 hours. 2 parts heptane is added to 100 g of this silica.
00 ml and butyl lithium in heptane (1 mM /
(100 ml) was added and reacted at room temperature for 1 hour. After separating silica from the reaction slurry solution by filtration and washing with heptane,
Inorganic Chemistry, 1985
Annually, 40 mM of dicyclopentadienyldichlorosilane prepared according to the method described in Vol. 24, page 2539 was added as a solution of 200 ml of heptane at room temperature and reacted for 1 hour. The solid was separated from the reaction slurry solution by filtration, and 300 ml of a tetrahydrofuran solution was added twice and heated at 80 ° C. to dissolve and separate lithium chloride. From the infrared absorption spectrum analysis of the solid, it was found that the hydroxyl groups on the silica surface had disappeared and that cyclopentadienyl groups were present.
Next, 200 ml of heptane and 40 ml of a heptane solution of butyllithium (1 mM / ml) were added to the solid and reacted for 1 hour at room temperature, and then the solid was separated from the reaction slurry solution by filtration and washed with heptane. Finally, 300 m of a tetrahydrofuran solution containing 10.0 mg of zirconium tetrachloride.
1 was added at room temperature and reacted for 1 hour. The solid was separated by filtration from the reaction slur solution, washed with tetrahydrofuran and dried to obtain a Zr compound-supported solid. The content of zirconium per 1 g of the solid was 0.18 mg atom. This solid 5
g is methylalumoxane (manufactured by Tosoh Akzo) 10
Contact treatment was performed with a 0 mM toluene solution at room temperature for 1 hour. The solid was separated from the reaction slurry solution by filtration, washed with tetrahydrofuran and dried to obtain a solid catalyst.

[Polymerization of Ethylene] The above solid catalyst (Z
r: 0.002 mg atom) was added to a 2 L autoclave equipped with a glass ampoule, and heptane 60 was added.
0 ml, triethylaluminum 0.2 mM, hydrogen 0.
It is introduced at 5 kg / cm ² and the content of the autoclave is adjusted to 80
The temperature was raised to ° C. Ethylene was introduced up to 10 kg / cm ² , the glass ampoule was crushed, and polymerization was carried out at 10 kg / cm ² for 1 hour while continuously feeding ethylene at 80 ° C. Polymerization activity is 44 kg per 1 mg atom of zirconium
(1 hr), and the obtained spherical polymer had a bulk specific gravity of 0.37 g / cm ³ , M. I. Is 5.9g / 10mi
n. , Mw / Mn was 2.5.

Example 2 [Slurry copolymerization of ethylene and 1-butene] Butene-
Polymerization was performed in the same manner as in Example 1 except that 15 ml of 1 was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and 1-butene. The polymerization activity was 70 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer was
The butene content is 5.12 mol%, the density is 0.916, the bulk specific gravity is 0.37 g / cm ³ , and the M. I. Is 6.8g / 10
min. , Mw / Mn was 3.5.

Example 3 [Slurry copolymerization of ethylene and 1-butene] Butene-
Polymerization was performed in the same manner as in Example 1 except that 30 ml of 1 was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and 1-butene. The polymerization activity was 78 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer was
Butene content is 10.3 mol%, density is 0.910, bulk specific gravity is 0.35 g / cm ³ , M. I. Is 10.9g / 1
0 min. , Mw / Mn was 3.4.

Example 4 Ethylene was used in the same manner as in Example 1 except that methylalumoxane 50 mM and triethylaluminum 50 mM were used in the contact treatment of the solid, and methylalumoxane 0.1 mM and triethylaluminum 0.1 mM were used during the polymerization. Was polymerized. Polymerization activity is 1 mg zirconium
It was 40 kg (1 hr) per atom, and the obtained spherical polymer had a bulk specific gravity of 0.35 g / cm ³ , M. I. Is 6.3 g / 10 min. , A spherical polymer having an Mw / Mn of 2.9 was obtained.

Example 5 [Slurry copolymerization of ethylene and 1-butene] Butene-
Polymerization was performed in the same manner as in Example 4 except that 15 ml of 1 was added and the polymerization time was 15 minutes to obtain a copolymer of ethylene and 1-butene. The polymerization activity was 62 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer was
Butene content is 4.51 mol%, density is 0.918, bulk specific gravity is 0.36 g / cm ³ , M. I. Is 7.2 g / 10
min. , Mw / Mn was 3.1.

Example 6 [Slurry copolymerization of ethylene and 1-butene] Butene-
Polymerization was performed in the same manner as in Example 1 except that 30 ml of 1 was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and 1-butene. The polymerization activity was 69 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer was
Butene content is 9.89 mol%, density is 0.910, bulk specific gravity is 0.35 g / cm ³ , M. I. Is 8.0 g / 10
min. , Mw / Mn was 3.3.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for preparing a solid catalyst for olefin polymerization of the present invention.

Claims (1)

[Claims] 1. A transition metal compound-supported solid in which one or more ligands of a transition metal compound of group IV or V of the periodic table is chemically bonded to an inorganic compound carrier or an organic polymer compound carrier, A solid catalyst for olefin polymerization, which has been subjected to a contact treatment with an aluminum oxy compound and / or an organic aluminum compound.