JPH0687923A - Solid catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To provide acatalyst composed of a specified transition metal compound supported on a polysiloxane, excellent in shape, having a narrow compositional distribution and a narrow molecular weight distribution, exhibiting a high polymerization activity and useful, e.g. for production of an olefin copolymer, etc., excellent in mechanical properties. CONSTITUTION:The catalyst is a transition metal compound belonging to IV or V group in the periodic table supported on a polysiloxane the substitute groups of which constitutes one or more ligands of the transition metal compound.

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, can obtain olefin polymers having narrow molecular weight distribution and compositional distribution in copolymerization and excellent physical properties. 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, and JP-A-61-108610.
JP-A No. 61-296008, JP-A-63-501369, JP-A-1-207303, JP-A-1-503715,
2-503687, Japanese Patent Laid-Open No. 2-170805, Special Table 3-5022
In JP 10 and JP-A 3-234710, a transition metal compound is supported on a porous inorganic compound carrier, or,
A catalyst system in which the amount of the aluminum oxy compound used is reduced by supporting the organic aluminum oxy compound and / or the organic aluminum compound 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]

DISCLOSURE OF THE INVENTION The present invention provides a solid catalyst comprising a group IV or V transition metal compound of the periodic table supported on a polysiloxane, wherein one or more of the ligands of the transition metal compound are It relates to a solid catalyst for olefin polymerization, which is a substituent of polysiloxane.

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 transition metal compound-supported solid catalyst in which a silicon atom of polysiloxane is chemically bonded to a ligand of a transition metal compound, and the ligand itself is a substituent of the polysiloxane.

The polysiloxane used in the present invention is-(SiR ¹
It is a silicon polymer having a siloxane bond represented by R ² O) _n- . In the present invention, at least a part of R ¹ and / or R ² needs to be a ligand capable of coordinating to a transition metal compound. Other R ¹ and R ² are usually preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Further, a branched or crosslinked polysiloxane in which some of the substituents R ¹ and / or R ² itself is a polysiloxane group and hardly soluble or insoluble in these organic solvents is also preferable.

Examples of the ligand having the ability to coordinate to a transition metal compound include cyclopentadienyl group, alkyl-substituted cyclopentadienyl group such as methyl, dimethyl and pentamethyl, indenyl group, cyclic unsaturated such as fluorenyl group. Hydrocarbon groups are preferred. In the present invention, these cyclic unsaturated hydrocarbon groups are directly chemically bonded to Si as a substituent of polysiloxane. Further, it is also possible to employ those in which the cyclic unsaturated hydrocarbon group forms a bond with Si of polysiloxane through a general hydrocarbon group. Also, the same Si
It is particularly preferable that two or more different types of cyclic unsaturated hydrocarbon groups, which are the same or different, are bonded to each other as a substituent. In this case, 2
A cyclic unsaturated hydrocarbon group, together with Si, constitutes a bridging ligand.

In the present invention, the ligand as the substituent of the polysiloxane also includes a ligand which constitutes a so-called bridged ligand containing two or more of the above cyclic unsaturated hydrocarbon groups. In this case, two or more cyclic unsaturated hydrocarbon groups are alkylene groups, substituted alkylene groups, silanylene groups, substituted silanylene groups, silaalkylene groups, substituted silaalkylene groups, oxasilanylene groups, substituted oxasilanylene groups, oxasilaalkylene groups, substituted A bridge type ligand bonded to an oxasilaalkylene group or the like can be mentioned. Hydrocarbon groups or ether groups are suitable as the substituents at the bridging site of these ligands. The bridging ligand and Si of the polysiloxane chain are suitable for the bridging site or this site. It is preferable to bond via a substituent.

Further, as a bridging ligand having a cyclic saturated hydrocarbon group at one end and N, P, and O at the other end, the cyclic saturated hydrocarbon group is an aminosilyl group, a monosubstituted aminosilyl group, or a phosphinosilyl group. , Mono-substituted phosphinosilyl groups and those bonded to oxysilyl groups. These ligands are preferably bonded to Si of the polysiloxane via the substituent of the silyl group.

The shape of the polysiloxane is not particularly limited, but spherical fine particles having an average particle diameter of 5 to 400 μ are preferable. The shape and particle size can be controlled arbitrarily in the well-known dehydration condensation reaction of hydroxysilane or in the method of preparing polysiloxane by condensation reaction involving hydrolysis of silicate, halogenosilane and the like.

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.
Is preferred. On the other hand, in the present invention, as the ligand forming the transition metal compound supported on the polysiloxane other than the substituent of the polysiloxane as the ligand,
Examples thereof include 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.

In the method for producing a solid catalyst for olefin polymerization in which one or more of the ligands of the transition metal compound is a substituent of polysiloxane in the present invention, first, a substituent of the transition metal compound as a ligand is usually used. It is possible to employ a method for producing a polysiloxane-supported transition metal compound in which a polysiloxane having ## STR3 ## is prepared and then a precursor of the transition metal compound is coordinated with a substituent of the polysiloxane. For example, the following methods can be mentioned.

First, cyclic unsaturated hydrocarbons and the periodic table
The metal salt is formed by reaction with an organometallic compound of Group I to III. Next, by reacting the metal salt with a silane compound having a halogen atom or an RO group (R represents a hydrocarbon group having 1 to 16 carbon atoms), a substituent as a ligand of the transition metal compound is obtained. A monomer for producing polysiloxane is synthesized.
It is desirable to dissolve and separate the halide or hydrocarbyl oxydide of an organometallic group I to III produced in this manufacturing process with an ether solvent such as THF.

In the above-mentioned method for producing a solid catalyst, the organometallic compounds of Groups I to III of the Periodic Table are Li, Na,
Alkyl, aryl or alkyl halides such as Mg or Al are preferred. The precursor of the transition metal compound coordinated to the polysiloxane having a substituent as a ligand is represented by the general formula MX _m (OR) _n R _p (wherein R is a carbon number of 1 to 10).
Hydrocarbon group, X is a halogen atom or a hydrogen atom, m + n + p is the maximum valence of the transition metal compound, m + n
> 1), a halide of a transition metal of Group IV or V of the periodic table, a hydrocarbyl oxyhalide, a hydrocarbyloxyhalide, a hydrocarbyloxyhydrocarbyl halide, a hydrocarbyl halide or a hydrocarbyloxyhydrocarbyl halide. You can

In order to coordinate a precursor of a transition metal compound, a substituent as a ligand of polysiloxane is reacted with an organometallic compound of Group I to III of the periodic table in an ether solvent to form a metal salt. And then can react with the precursor. Also in this case, it is desirable to dissolve and separate the organometallic halide or hydrocarbyl oxydide produced in the reaction with an ether solvent.

The solid catalyst for olefin polymerization of the present invention can be used to polymerize olefins, for example, by the following method. (1) An olefin is polymerized in the presence of the solid catalyst and an organoaluminum oxy compound and / or an organoaluminum compound as a cocatalyst. (2) After subjecting the solid catalyst to a contact treatment with an organoaluminum oxy compound and / or an organoaluminum compound as an activator, an olefin is polymerized in the presence of the contact treated solid catalyst. (3) After the contact treatment of the solid catalyst with an organoaluminum oxy compound and / or an organoaluminum compound as an activator, the contact treatment solid catalyst and an organoaluminum oxy compound and / or an organoaluminum compound as a co-catalyst The olefin is polymerized in the presence.

The organoaluminum oxy compound as a co-catalyst used in the above olefin polymerization or copolymerization is a linear or cyclic polymer represented by the general formula (-Al (R) O-) _n . , R is a hydrocarbon group having 1 to 10 carbon atoms, and a part of R 1 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 has the general formula AlR
_r X _3-r (in the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom or a hydrogen atom, and r is 0 <r ≤3). Examples thereof include trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, alkenylaluminum, dialkylhydroaluminum and sesquialkylhydroaluminum.

The olefin polymerization in the present invention can be applied to any polymerization method such as a stirring type or fluidized bed type gas phase method, a slurry method, a high temperature and high pressure method, and a 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.

In the present invention, the slurry method in an inert hydrocarbon solvent or the stirred or fluidized bed gas phase polymerization method is usually carried out at 5 to 100 ° C. for 20 to 300 minutes, and the transition of the organoaluminum in the solid catalyst is carried out. It can be carried out under the conditions that the atomic ratio (Al / M) of the metal 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., 5 to 600 seconds,
The atomic ratio of transition metal in the solid organoaluminum catalyst is 5
It can be carried out under a polymerization pressure condition of ˜200, 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. Pre-polymerization is, for example, usually 5 to 5 in a slurry method in an inert hydrocarbon solvent.
It can be carried out at 80 ° C. for 5 to 60 minutes under the conditions that the atomic ratio of transition metal to aluminum in the solid catalyst 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 ethylene, propylene and butene.
Examples thereof include aliphatic monoolefins such as -1,4-methylpentene-1, hexene-1 and octene-1, and cyclic monoolefins such as cyclopentene, cyclohexene and norbornene. Further, in the above-mentioned olefin polymerization and copolymerization, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexene, or
Non-conjugated linear or cyclic diolefins such as 1,5-hexadiene can be copolymerized.

[0025]

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.

[0026]

Examples In the examples, "polymerization activity" means the polymer yield (k per 1 g of transition metal of the solid catalyst used in the polymerization reaction.
g). "MI" means 2.16 kg according to ASTM D-1238
Melt index of the polymer measured at 190 ° C. under a load of / cm ² . 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. Content of transition metal in solid catalyst is determined by colorimetric method, content of comonomer in copolymer is H
-Measured by 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 [Synthesis of Silane Compound] A solution prepared by dissolving 6.6 g (0.1 M) of cyclopentadiene in 100 ml of tetrahydrofuran was -50 ° C.
With stirring, BuLi 0.1M (heptane solution with a concentration of 1.6M / L),
It dripped over 30 minutes. After the dropping, raise the temperature to room temperature,
A slurry solution of cyclopentadienyl lithium was obtained.
Tetrachlorosilane 8.45 g (0.
The solution in which 05M) was dissolved was added dropwise at 25 ° C. After the dropping, triethylamine 0.11M dissolved in 50 ml of methanol was gradually added. After stirring for 2 hours, the solution was concentrated under reduced pressure, and then the reaction solution was extracted with 30 ml of toluene. The 90 ° C / 4 mmHg component was separated from the toluene solution by distillation. This component was found to be dicyclopentadienyldimethoxysilane Cp ₂ Si (OMe) ₂ by elemental analysis, 1 H-NMR and Mass analysis.

[Synthesis of Polysiloxane] Obtained as described above
Cp ₂ Si (OMe) ₂ 0.22 g (1.0 mM) and tetramethoxysilane 7.6
g (50 mM) was dissolved in 20 ml of heptane, 1 ml of a 1N aqueous hydrochloric acid solution was added, and the mixture was stirred at 50 ° C. for 15 hours for reaction. The produced solid was filtered, separated, washed with toluene, and then dried under reduced pressure to obtain powdery polysiloxane. By IR and elemental analysis, this polysiloxane was a crosslinked polymer having a cyclopentadienyl group and a methoxy group and insoluble in an organic solvent.

[Preparation of Solid Catalyst] 2 g of the polysiloxane as the carrier obtained above was made into a slurry of 10 ml of tetrahydrofuran. BuLi 2mM was added dropwise to this slurry at -10 ° C, and the temperature was raised to room temperature to lithiate the cyclopentadienyl substituent of the polysiloxane. Next, 5 ml of tetrahydrofuran was added to the powder obtained by filtering, separating and washing with tetrahydrofuran, and further tetrachlorozirconium was added.
Add 5 ml of a 0.25 mM tetrahydrofuran solution at room temperature.
The reaction was carried out for 2 hours. A solid was filtered from the slurry, separated, washed with tetrahydrofuran, and then dried to obtain a polysiloxane-supported solid catalyst. The amount of zirconium supported on this solid catalyst was 0.91% by weight.

[Polymerization of Ethylene] The above solid catalyst (Zr
Containing 0.008 mg atom) and methylalumoxane (Tosoh
To a 2 L autoclave equipped with a glass ampoule in which 1 mL of a toluene solution containing 1.6 mM of Akzo Co., Ltd. was introduced, 600 ml of heptane and 1.0 kg / cm ^{2 of} hydrogen were introduced, and the content of the autoclave was heated to 85 ° C. 10 kg / c of ethylene
After introducing up to m ² , the glass ampoule was crushed, and polymerization was carried out at 10 kg / cm ² for 1 hour while continuously feeding ethylene at 85 ° C. Polymerization activity is 45 kg (1 hr) per 1 mg atom of zirconium
The obtained spherical polymer has a bulk specific gravity of 0.35 g / c.
m ³ , MI was 9.5 g / 10 min. and Mw / Mn was 2.9.

Example 2 [Slurry copolymerization of ethylene and butene-1] Butene-1
Polymerization was performed in the same manner as in Example 1 except that 15 ml was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and butene-1.
The polymerization activity was 70 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical copolymer had a butene content of 5.56 mol%, a density of 0.920, a bulk specific gravity of 0.34 g / cm ³ , and an MI of 10.1.
The g / 10 min. and Mw / Mn were 3.6.

Example 3 [Slurry copolymerization of ethylene and butene-1] Butene-1
Polymerization was carried out in the same manner as in Example 1 except that 30 ml was added and the polymerization time was 15 minutes to obtain a copolymer of ethylene and butene-1.
The polymerization activity was 79 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical copolymer had a butene content of 9.68 mol%, a density of 0.931, a bulk specific gravity of 0.36 g / cm ³ , and an MI of 11.5.
The g / 10 min. and Mw / Mn were 3.3.

Example 4 [Polymerization of ethylene] 1 g of the solid catalyst prepared in Example 1 was subjected to contact treatment with a toluene solution of 40 mM of methylalumoxane at room temperature for 1 hour, and then a solid catalyst (containing 0.008 mg of Zr) was enclosed. To a 2 L autoclave equipped with a glass ampoule, 600 ml of heptane, 0.8 mM of triethylaluminum,
Introduce hydrogen up to 1.0 kg / cm ² and remove the autoclave contents to 85
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 85 ° C. The polymerization activity was 39 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer had a bulk specific gravity of 0.36 g / cm ³ and an MI of 8.7 g / 10 mi.
n., Mw / Mn was 3.1.

Example 5 [Slurry copolymerization of ethylene and 1-butene] Butene-1
Polymerization was performed in the same manner as in Example 4 except that 15 ml was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and butene-1.
The polymerization activity was 51 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical copolymer had a butene content of 5.58 mol%, a density of 0.919, a bulk specific gravity of 0.35 g / cm ³ , and an MI of 10.2.
The g / 10 min. and Mw / Mn were 3.7.

Example 6 [Slurry copolymerization of ethylene and butene-1] Butene-1
Polymerization was performed in the same manner as in Example 4 except that 30 ml was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and butene-1.
The polymerization activity is 60 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer has a butene content of 10.2 mol%, a density of 0.912, a bulk specific gravity of 0.34 g / cm ³ , and an MI of 12.3 g /
10 min., Mw / Mn was 3.9.

Example 7 [Polymerization of ethylene] Polymerization was carried out in the same manner as in Example 1 except that 0.8 mM of methylalumoxane and 0.8 mM of triethylaluminum were used in place of 1.6 mM of methylalumoxane to polymerize ethylene and butene. A copolymer of -1 was obtained. Polymerization activity was 50 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer had a bulk specific gravity of 0.33 g / cm ³ and an MI of 1
0.3g / 10min., Mw / Mn was 3.1.

Example 8 [Slurry copolymerization of ethylene and 1-butene] Butene-1
Polymerization was performed in the same manner as in Example 7 except that 15 ml was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and butene-1.
The polymerization activity was 55 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical copolymer had a butene content of 4.99 mol%, a density of 0.921, a bulk specific gravity of 0.35 g / cm ³ , and an MI of 11.5.
The g / 10 min. and Mw / Mn were 3.5.

Example 9 [Slurry copolymerization of ethylene and butene-1] Butene-1
Polymerization was performed in the same manner as in Example 7 except that 30 ml was added and the polymerization time was changed to 15 minutes to obtain a copolymer of ethylene and butene-1.
The polymerization activity is 63 kg (1 hr) per 1 mg atom of zirconium, and the obtained spherical polymer has a butene content of 9.85 mol%, a density of 0.914, a bulk specific gravity of 0.36 g / cm ³ , and an MI of 13.3 g / cm ³ .
10 min., Mw / Mn was 3.7.

[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 solid catalyst comprising a group IV or V transition metal compound of the periodic table supported on a polysiloxane, wherein one or more of the ligands of the transition metal compound is a substituent of the polysiloxane. Solid catalyst for olefin polymerization.