JPH072783B2 - Olefin polymerization catalyst component - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Ziegler-type catalytic transition metal or solid component which provides a polymer having high activity and good polymer properties.

Conventionally, when a magnesium compound such as magnesium halide, magnesium oxyhalide, dialkyl magnesium, alkyl magnesium halide, magnesium alkoxide, or a complex of dialkyl magnesium and organic aluminum is used as a carrier for a transition metal compound such as a titanium compound, it becomes a highly active catalyst. It is known that many inventions have been proposed.

In these prior arts, the catalytic activity is high to some extent, but the polymer properties of the polymer produced are not sufficient, and improvement is desired. Polymer properties are extremely important in slurry polymerization, gas phase polymerization and the like. Poor polymer properties tend to cause polymer adhesion in the polymerization tank, poor extraction of the polymer from the polymerization tank, and the like. Also, the polymer concentration in the polymerization tank is closely related to the polymer properties,
If the polymer properties are not good, the polymer concentration in the polymerization tank cannot be increased. The fact that the polymer concentration cannot be increased is a great disadvantage in industrial production.

In addition, in the production of many conventional catalyst components, a large amount of transition metal component is used, and so-called “transition metal component basic unit” is used.
Is bad. This is a great disadvantage in producing the catalyst. That is, many transition metal components that are not contained as catalyst components need to be removed from the catalyst components, which necessitates many solvents and the like, leading to an increase in the production cost of the catalyst. Further, it is necessary to decompose unnecessary transition metal components, but halogen gas, hydrogen halide, etc. are often generated during the decomposition treatment, which is extremely bad in terms of environmental hygiene. Therefore, it is desired to improve the basic unit of the transition metal component.

BACKGROUND ART According to Japanese Patent Publication No. 51-37195, a method is proposed in which a magnesium halide or the like is reacted with titanium tetraalkoxide, and further an organoaluminum halide is reacted. According to JP-A-54-16393, magnesium tetrahalide is reacted with magnesium halide or the like,
Further, a method of reacting a halogen-containing compound with a reducing compound has been proposed. When olefins such as ethylene are polymerized using the catalysts produced by these methods, the catalytic activity shows a certain value, but the properties of the produced polymer do not seem to be good.

Incidentally, a Ziegler type catalyst is well known as a catalyst for olefin stereoregular polymerization, and it is also well known that various methods have been proposed in order to further improve its activity and stereoregularity.

Among these various improving methods, a method having a particularly remarkable improving effect on the activity is to introduce a magnesium compound into a solid component (Japanese Patent Publication No.
No. 12105, Japanese Patent Publication No. 47-41676, and Japanese Patent Publication No. 47-46269
No. However, when olefins such as propylene are polymerized using the catalysts produced by these methods, the activity shows a very high value, but the stereoregularity of the produced polymer is remarkably lowered, and the olefin stereoregularity is decreased. It is also known that practical value as a polymerization catalyst is greatly lost.

Therefore, in the olefin polymerization using a Ziegler type catalyst containing a magnesium compound, various methods for improving the stereoregularity of the produced polymer have been proposed (Japanese Patent Laid-Open No. S60-18753).
47-9842, 50-126590, 51-57789, etc.).

These methods are commonly characterized in that a solid catalyst component containing a titanium compound and a magnesium halogen compound further contains an electron donor such as an ester or an amine.

On the other hand, a method of adding a silicon compound, alcohol or the like as a third additive to the solid catalyst component in addition to the electron donor (Japanese Patent Application Laid-Open Nos. 50-108385, 52-100596 and 52-104593).
No. gazettes) are also known.

Although such a method significantly improves the stereoregularity of the active polymer and the produced polymer, the decatalysis step of the produced polymer and the extraction step of the amorphous polymer have not yet been eliminated. Also, the properties of the polymer produced are not sufficient.

SUMMARY OF THE INVENTION The purpose of the present invention is to provide a solution to the above points, and to achieve this object by a supported transition metal catalyst component prepared in a specific embodiment.

Therefore, the catalyst component for olefin polymerization according to the present invention is characterized by being a contact product of the following component (A ₁ ), component (A ₂ ) and component (A ₃ ).

Component (A ₁ ) The contact product of the magnesium dihalide with titanium tetraalkoxide and / or its polymer has the general formula
A solid composition obtained by contacting a halogenating agent selected from SiX ₄ (where X is a halogen).

Component (A ₂ ) Ortho-C ₆ H ₄ (COCl) ₂ or cyclo-C ₆ H ₁₀ (COCl)
_Two .

Component (A ₃ ) At least one of the following components (a) and (b).

(A) A compound represented by the general formula TiX ₄ (where X is a halogen), and (b) a compound represented by the general formula SiX ₄ (where X is a halogen).

Effects When the solid catalyst component according to the present invention is used as a transition metal component of a Ziegler catalyst to polymerize an olefin, a polymer having high activity and excellent polymer properties can be obtained.
For example, considering the polymer bulk specific gravity, which is one measure of polymer properties, 0.40 (g / cc) or more is possible, and 0.45 (g / cc) or more is also possible.

DETAILED DESCRIPTION OF THE INVENTION Catalyst Component The catalyst component of the present invention is a contact product of the following component (A ₁ ), component (A ₂ ) and component (A ₃ ).

Ingredient (A ₁ ) (1) Composition Ingredient (A ₁ ) is selected from the general formula SiX ₄ (where X is halogen) in the contact product of magnesium dihalide with titanium tetraalkoxide and / or its polymer. It is a solid composition obtained by contacting a halogenating agent.
At present, its content has not been sufficiently analyzed, but this component (A ₁ ) contains titanium, magnesium and halogen.

(2) Production Component (A ₁ ) is produced by contacting magnesium dihalide with titanium tetraalkoxide and / or its polymer and then with a halogenating agent.

(A) Magnesium dihalide For example, there are MgF ₂ , MgCl ₂ , MgBr ₂ , and the like.

(B) a titanium tetraalkoxide and a polymeric titanium tetraalkoxide, _{e.g., Ti (OC 2 H 5)} 4, Ti (O-iC 3 H 7) 4, Ti (O-nC 4 H 9) 4, Ti _{(O-nC 3 H 7)} 4, Ti (O-iC 4 H 9) 4, Ti [OCH ₂ CH (CH _{3) 2] 4,} Ti [OC (CH _{3) 3] 4,} Ti (O-nC _{5 H 11) 4, Ti (} O-nC 6 H 13) 4, Ti (O-nC 7 H 15) 4, Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] _4, and the like. Among these, Ti (OC ₂ H ₅ ) ₄ and Ti (O-nC ₄ H ₉ ) ₄ are preferable.

As a polymer of titanium tetraalkoxide, there is a polymer represented by the following formula.

Here, R ^{1 to} R ⁴ are the same or different hydrocarbon residues, preferably an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, particularly an aliphatic hydrocarbon having 2 to 6 carbon atoms. n represents a number of 2 or more, particularly a number of up to 20. It is desirable that the value of n be selected so that the polytitanate can be used as it is or as a solution in liquid form for the step of contacting with other components. The suitable n for handling is 2 to 14, preferably 2 to 10,
It is a degree. Specific examples of such polytitanate include normal butyl polytitanate (n = 2 to
10), hexyl polytitanate (n = 2 to 10), normal octyl polytitanate (n = 2 to 10), and the like.
Of these, normal butyl polytitanate is preferred.

(C) Halogenating agent The halogenating agent used in the present invention is selected from the general formula SiX ₄ (where X is a halogen).

This compound acts by presumably halogenating the liquid product formed by contacting the magnesium dihalide with the titanium alkoxide and / or its polymer to precipitate it as a solid composition. Therefore, this compound is preferably not solid.
If it is a solid compound, use it as a solution.

Typical halogens are fluorine, chlorine, bromine and iodine. Silicon is an element that should be combined with halogen to form a halide. Therefore, specific examples of the halogenating agent include SiF ₄ , SiCl ₄ , and SiB.
There are r ₄ and Sil ₄ . Of these, SiCl ₄ is particularly preferable.

(D) Contact of each component (i) Amount ratio The amount of each component used may be any amount as long as the effect of the present invention can be recognized, but it is generally preferably within the following range.

The amount of titanium tetraalkoxide and / or its polymer used is preferably in the range of 0.1 to 10 in terms of molar ratio to magnesium dihalide, preferably in the range of 1 to 4, and more preferably in the range of 2 to 3. Within the range of.

The amount of the halide used is preferably within a range of 0.1 to 50, and more preferably within a range of 1 to 10, in terms of molar ratio with respect to the titanium tetraalkoxide and / or its polymer.

(Ii) Contact Method The contact of the magnesium dihalide with the titanium tetraalkoxide and / or the polymer thereof in the first step is preferably carried out so that the magnesium dihalide is dissolved. Then, the contact with the halide in the second step is preferably carried out so that the halide is added to this solution to precipitate the solid composition.

It is preferable that each step is performed at a temperature in the range of −100 ° C. to 200 ° C. for about 10 minutes to 20 hours. It is preferable to perform stirring so that sufficient contact can be secured. Contacting can be performed in the presence of a dispersion medium, and is also preferable. A suitable dispersion medium can be selected from those exemplified as those to be used in the contact of the components (A ₁ ) to (A ₃ ).

The component (A ₁ ) prepared as described above is usually washed with a solvent as described above as a dispersion medium to remove the unreacted liquid component.

Component (A ₂ ) Component (A ₂ ) is ortho-C ₆ H ₄ (COCl) ₂ or cyclo-
It is C ₆ H ₁₀ (COCl) ₂ .

Component (A ₃ ) Component (A ₃ ) is at least one of the following components (a) and (b).

The component (a) is a compound represented by the general formula TiX ₄ (where X is a halogen). As a specific example, TiCl ₄ , TiBr ₄ ,
and so on.

The component (b) is a compound represented by the general formula SiX ₄ (where X is a halogen). Specific examples include SiCl ₄ , SiBr ₄ ,
and so on.

Synthesis of Catalyst Component The catalyst component of the present invention can be synthesized by bringing the components (A ₁ ) to (A ₃ ) into contact with each other.

1) Amount Ratio The amount of each component used is arbitrary as long as the effects of the present invention are recognized, but generally the following ranges are preferable.

The amount of the component (A ₂ ) used is preferably in the range of 1 × 10 ⁻³ to 10 with respect to the magnesium dihalide constituting the component (A ₁ ), preferably 1 × 10 ⁻² to 1. It is within the range.

The amount of component (A ₃ ) used is preferably in the range of 1 × 10 ^{−2 to} 100, and more preferably in the range of 0.1 to 10, in molar ratio with respect to the magnesium dihalide.

2) Contact method The contact of each component can be performed by adding the above-mentioned component (A ₁ ) to the component (A ₂ ) and the component (A ₃ ) at a time or stepwise between the components or within the components (washing between each stage). It may be performed).

The contact may be generally performed within a temperature range of -100 ° C to 200 ° C.

The contact time is usually about 10 minutes to 20 hours.

The solid component (A ₁ ) and the components (A ₂ ) to (A ₃ ) are preferably contacted with stirring, and a ball mill, a vibration mill,
It is also possible to bring them into contact with each other by mechanically pulverizing them. The order of contact is as long as the effect of the present invention is recognized.
It can be arbitrary.

The contact between the solid component (A ₁ ) and the component (A ₂ ) to the component (A ₃ ) is
It can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium at that time include hydrocarbons, halogenated hydrocarbons, dialkylsiloxanes and the like. Specific examples include hexane, heptane, toluene, cyclohexane, n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, dimethylpolysiloxane, methyl-phenylpolysiloxane, and the like.

The catalyst component of the present invention obtained as described above is usually washed with a solvent as described above as a dispersion medium to remove the unreacted liquid component.

Olefin Polymerization Catalyst Formation The catalyst components of the present invention can be used in olefin polymerization in combination with a cocatalyst organometallic compound. Any of the organometallic compounds of metals of Groups I to IV of the Periodic Table known as cocatalysts can be used.

As the cocatalyst, an organoaluminum compound is particularly preferable. Specific examples of the organic aluminum compound include the general formula ▲ R ⁶ _3-n ▼ AlX _n or ▲ R ⁷ _3-m ▼ Al (OR ⁸ ) _m (wherein R ⁶ , R ⁷ and R ⁸ are the same or different. 1 to 1 carbon atoms
About 20 hydrocarbon residues or hydrogen, X is a halogen, and n and m are numbers 0n <2 and 0m1, respectively. ). The following are specific examples. (A) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc.,
(B) Diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride,
Alkyl aluminum halides such as (c) Diethyl aluminum hydride, Dialkyl aluminum hydrides such as diisobutyl aluminum hydride,
(D) Alkyl aluminum alkoxides such as diethyl aluminum ethoxide, diethyl aluminum butoxide, diethyl aluminum phenoxide, and the like.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds such as ▲ R ⁹ _3-a ▼ Al (OR ¹⁰ ) _a (1
a3, R ⁹ and R ¹⁰ are the same or different hydrocarbon residues having about 1 to 20 carbon atoms. It is also possible to use an alkylaluminum alkoxide represented by the formula (1). For example, combination of triethylaluminum and diethylaluminum ethoxide, combination of diethylaluminum monochloride and diethylaluminum ethoxide, combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum chloride. It can be used in combination with.

The amount of these organometallic compounds used is not particularly limited,
The weight ratio with respect to the solid catalyst component of the present invention is preferably within the range of 0.5 to 1000.

In order to improve the stereoregularity of an olefin polymer having 3 or more carbon atoms, it is effective to add and coexist an electron donating compound such as an ether, an ester, an amine or a silane compound during the polymerization. The amount of the electron-donating compound used for such a purpose is 0.00 based on 1 mol of the organoaluminum compound.
It is 1 to 2 mol, preferably 0.01 to 1 mol. Specific examples of the electron donating compound used for this purpose include, for example,
JP-A-55-127408, JP-A-56-139511, JP-A-57-
No. 63310 is disclosed.

Olefin The olefin polymerized by the catalyst system of the present invention has the general formula R-CH
CH ₂ (wherein R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms and may have a branching group). Specifically, ethylene, propylene,
There are olefins such as butene-1, pentene-1, hexene-1, 4-methylpentene-1. Preferred are ethylene and propylene. In the case of these polymerizations, it is possible to carry out up to 50% by weight, preferably 20% by weight, of the above-mentioned olefins with ethylene, and with propylene up to 30% by weight of the said olefins, especially with ethylene. Can be copolymerized. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefin) can also be performed.

Copolymerization The catalyst system of the present invention is not only applied to ordinary slurry polymerization, but is also applied to liquid phase solventless polymerization, solution polymerization, or gas phase polymerization method substantially without using a solvent. . Further, it is also applicable to a system in which continuous polymerization, batch polymerization or preliminary polymerization is carried out. As a polymerization solvent in the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture. The polymerization temperature is from room temperature to about 200 ° C, preferably 50 ° C to 150 ° C,
Hydrogen can be supplementarily used as a molecular weight regulator at that time.

N of dehydrated and deoxygenated synthetic thoroughly purged with nitrogen flask Experiment Example 1 (1) component (A ₁₎
Introducing 100 ml of heptane, then MgCl ₂ 0.1
_{Mol, Ti (O-nC 4 H} 9) 4 and then 0.2 mol introduced and reacted for 2 hours at 95 ° C.. After the reaction was completed, the temperature was lowered to 30 ° C and SiCl ₄ 0.4
Mols were introduced over 1 hour and reacted at 50 ° C. for 2 hours.
After completion of the reaction, the reaction product was washed with n-heptane, and a part thereof was taken out to measure the Ti content, which was 5.6% by weight.

(2) Synthesis of catalyst component n was dewatered and deoxygenated in a flask that had been sufficiently replaced with nitrogen.
— 100 ml of heptane was introduced, and 0.03 mol of the above-synthesized component (A ₁ ) was introduced in terms of Mg atom. Then n
− Mix 25 ml of heptane with 0.004 mol of ortho-C ₆ H ₄ (COCl) ₂ and mix at 30 ° C at 30 ° C.
It was introduced in minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, it was washed with purified n-heptane. Then TiCl ₄ 2
5 ml was introduced and reacted at 100 ° C. for 3 hours.
After completion of the reaction, it was washed with n-heptane to obtain a catalyst component. The Ti content of this catalyst component was measured and found to be 2.27 weight percent.

(3) Polymerization of propylene In a stainless steel autoclave having an internal volume of 1.5 liter equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum, 26.8 mg of diphenyldimethoxysilane, and The catalyst component synthesized above
Introduced 15 mg. Next, 60 ml of H ₂ was introduced, the temperature was raised and the pressure was increased, and the polymerization pressure was 5 kg / cmG and the polymerization temperature was 7
Polymerization was carried out under the conditions of 5 ° C. and polymerization time = 2 hours. After the polymerization was completed, the obtained polymer slurry was separated by filtration and the polymer was dried.

94.7 grams of polymer were obtained. On the other hand, from the excess fluid,
9 grams of polymer were obtained. From the boiling heptane extraction test, the total product II (hereinafter abbreviated as T-II) was 96.8% by weight. The MFR was 7.1 (g / 10 minutes) and the bulk density of the polymer was 0.421 (g / cc).

Was introduced into Example 2 (1) similarly synthesized component Synthesis Example -1 of the catalyst component (A ₁₎ in the same manner as Example -1 flask. Then 0.05 mol of SiCl ₄ to 3
The mixture was introduced at 0 ° C for 15 minutes and reacted at 70 ° C for 2 hours. After completion of the reaction, it was washed with n-heptane. Then, 25 ml of n-heptane was mixed with 0.004 mol of ortho-C ₆ H ₄ (COCl) ₂ and introduced at 70 ° C. for 30 minutes and reacted at 70 ° C. for 1 hour. After the reaction,
It was washed with n-heptane. Then, 25 ml of TiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane to obtain a catalyst component. The Ti content was 2.18 weight percent.

(2) Polymerization of propylene Under the polymerization conditions of Example-1, propylene was polymerized in exactly the same manner except that 26 mg of phenyltriethoxysilane was used instead of diphenyldimethoxysilane. 107.2 grams of polymer were obtained. T-
II = 96.9 weight percent, MFR = 6.4 (g / 10 min), polymer bulk density = 0.41 (g / cc).

In the synthesis of the catalyst component of Example 3 (1) Synthesis example of a catalyst component -1, ortho -C ₆ H
_The catalyst components were synthesized in exactly the same manner except that cyclo-C ₆ H ₁₀ (COCl) ₂ was used instead of ₄ (COCl) ₂ .
The Ti content of this catalyst component was 2.86 weight percent.

(2) Polymerization of Propylene Polymerization of propylene was carried out in exactly the same manner as in Example-1.
91.2 grams of polymer were obtained, T-II = 94.1 weight percent, MFR = 6.3 (g / 10 min), polymer bulk density = 0.41.
(G / cc).

In the synthesis of the catalyst component of Comparative Example 1 (1) Synthesis example of a catalyst component -1, using ZnCl ₄ instead of SiCl _4, C ₆ H instead of ortho -C ₆ H ₄ (COCl) ₂ Synthesis was performed in exactly the same manner except that ₅ COCl was used. The Ti content of this catalyst component was measured and found to be 2.73 weight percent.

(2) Polymerization of propylene Under the polymerization conditions of Example-1, the same procedure was carried out except that the amount of diphenyldimethoxysilane used was 53.6 mg. 77.2 grams of polymer were obtained. T-I.
I = 93.6 weight percent, MFR = 8.2 (g10 min), polymer bulk specific gravity = 0.41 (g / cc).

Comparative Example-2 A solid catalyst component was produced in the same manner as in Example-1 of JP-A-58-32604. Polymerization of propylene was carried out in the same manner as in Example 1 except that the obtained solid component was used. As a result, 7
3.6 grams of polymer were obtained, T-II = 93.6 weight percent, MFR = 8.6 (g / 10 min), polymer bulk specific gravity = 0.41.
(G / cc).

Comparative Example-3 A similar experiment was conducted except that benzoyl chloride was used in place of ethyl p-toluate (component (3)) in the production of the solid catalyst component of Example-1 of JP-A-58-32604. A solid catalyst component was synthesized. The Ti content of the obtained solid component is 3.
It was 12 weight percent.

Polymerization was performed in the same manner as the propylene polymerization in Example-1 except that the solid component obtained above was used. As a result, 7
9.2 grams of polymer was obtained, T-II = 93.3 weight percent, MFR = 8.7 (g / 10 min), polymer bulk specific gravity = 0.42 (g /
It was cc).

[Brief description of drawings]

FIG. 1 is intended to help the understanding of the technical content of the present invention regarding the Ziegler catalyst.

Claims (1)

[Claims] 1. A catalyst component for olefin polymerization, which is a catalytic product of the following component (A ₁ ), component (A ₂ ) and component (A ₃ ). Component (A ₁ ) The contact product of the magnesium dihalide with titanium tetraalkoxide and / or its polymer has the general formula
Solid composition obtained by contacting a halogenating agent selected from SiX ₄ (where X is halogen), component (A ₂ ) ortho-C ₆ H ₄ (COCl) ₂ or cyclo-C ₆ H ₁₀ (COCl)
₂ , component (A ₃ ) at least one of the following components (a) and (b), (a) a compound represented by the general formula TiX ₄ (where X is a halogen), (b) a general formula SiX ₄ (where X is X). Is a halogen).