JPH0694486B2 - Catalyst for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is a high-performance catalyst which acts highly active when subjected to the polymerization of olefins, and which can obtain a stereoregular polymer in a high yield. The component and the method for producing the catalyst, more specifically, a catalyst component for polymerization of olefins, a nitrogen-containing organic compound and an organic aluminum obtained by contacting a fatty acid magnesium, a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon and a titanium halide. The present invention relates to a catalyst for olefin polymerization, which comprises a compound.

[Conventional technology]

Conventionally, as a catalyst for olefin polymerization, a combination of a solid titanium halide as a catalyst component and an organoaluminum compound is well known and widely used. Since the yield of the polymer (hereinafter referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) is low, a so-called deashing step for removing the catalyst residue was unavoidable. Since this deashing process uses a large amount of alcohol or a chelating agent, a recovery device or a regenerating device for them is indispensable, and resources,
There are many energy and other incidental problems, and it is an important issue for those skilled in the art to solve the problem immediately. In order to eliminate this complicated deashing step, many studies have been made and proposed to increase the polymerization activity per catalyst component, especially titanium per catalyst component.

In particular, as a recent tendency, a transition metal compound such as titanium halide, which is an active component, is supported on a simple substance such as magnesium chloride, and when it is subjected to the polymerization of olefins, the polymerization activity per titanium in the catalyst component is dramatically increased. There are many proposals to raise the price.

[Problems to be solved by the invention]

However, the chlorine contained in magnesium chloride, which forms the mainstream as a carrier substance, has a drawback that it has an adverse effect on the produced polymer as well as the halogen element in titanium halides. Therefore, the effect of chlorine is virtually ignored. There was an unsolved part such as a high activity required, or the need to keep the concentration of magnesium chloride itself low.

The inventors of the present invention have disclosed that, in order to reduce the residual chlorine in the produced polymer while maintaining the polymerization activity per catalyst component and the yield of the stereoregular polymer at a high level, Japanese Patent Application No. 57-20
In 0454, a method for producing a catalyst component for polymerization of olefins was proposed, and the initial purpose was achieved. Further, when the polymerization of olefins, particularly the stereoregular polymerization of propylene, 1-butene and the like is industrially carried out, it is usually necessary to make an electron donating compound such as an aromatic carboxylic acid ester coexist in the polymerization system. It is indispensable in a catalyst that uses a catalyst component having a carrier of (1) as a carrier in combination with an organoaluminum compound. However, this aromatic carboxylic acid ester imparts an ester odor peculiar to the produced polymer, and its removal is a major problem in the art.

Further, in a so-called highly active supported catalyst, such as a catalyst using a catalyst component having magnesium chloride as a carrier,
Although the activity at the initial stage of the polymerization is high, the deactivation is large, which causes a problem in the process operation, and when it is necessary to prolong the polymerization time such as block copolymerization, it is practically impossible to use. In order to improve this point, for example, in JP-A-54-94590, a catalyst component is prepared by using magnesium dihalide as a starting material, and an organoaluminum compound, an organic carboxylic acid ester, and a compound having an M-O-R group. A method of using it for the polymerization of olefins has been shown, but since the organic carboxylic acid ester is used during the polymerization, the problem of the odor of the produced polymer has not been solved, and as can be seen from the examples. It requires very complicated operation, and it cannot be said that the one having sufficient performance is obtained in terms of performance and activity.

The inventors of the present invention have reached the present invention as a result of earnest research in order to solve the problems remaining in such conventional techniques, and make a proactive proposal.

[Means for solving problems]

That is, the features of the present invention are: (A) (a) magnesium fatty acid, (b) diester of aromatic dicarboxylic acid, (c) halogenated hydrocarbon, and (d) general formula TiX ₄ (where X is It is a halogen element.)
A catalyst component obtained by contacting with a titanium halide represented by (hereinafter sometimes simply referred to as titanium halide); (B) general formula A nitrogen-containing organic compound represented by the formula (wherein R is an alkyl group or an alkoxy group) (hereinafter simply referred to as a nitrogen-containing organic compound). (C) A catalyst for olefin polymerization comprising an organic aluminum compound is provided. .

As the fatty acid magnesium used in the present invention, saturated fatty acid magnesium is preferable, and magnesium stearate, magnesium octanoate, magnesium decanoate and magnesium laurate are particularly preferable.

The fatty acid magnesium is preferably used in a form in which water is removed as much as possible.

The aromatic dicarboxylic acid diester used in the present invention is preferably a phthalic acid or terephthalic acid diester, for example, dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, Examples thereof include dibutyl terephthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.

The halogenated hydrocarbon used in the present invention is preferably a chloride of an aromatic or aliphatic hydrocarbon that is liquid at room temperature, for example, propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane. , Trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride and the like, among which propyl chloride, dichloroethane, chloroform, carbon tetrachloride and methylene chloride are preferred.

Formula TiX ₄ used in the present invention (wherein X is a halogen element.) TiCl ₄ as a titanium halide represented by, TiBr _4, TiI ₄ but like among them TiCl ₄
Is preferred.

The nitrogen-containing organic compound used in the present invention is preferably one having an alkyl group or an alkoxy group having 1 to 10 carbon atoms.

Examples of the organoaluminum compound used in the present invention include trialkylaluminums, dialkylaluminum halides, alkylaluminum dihalides, and mixtures thereof. Among them, trialkylaluminums are preferable, and triethylaluminums and triisobutylaluminums are particularly preferable.

When obtaining the catalyst component of the present invention, the use ratio of each raw material constituting the catalyst component is arbitrary as long as it does not adversely affect the performance of the catalyst component to be produced, it is not particularly limited, The diester of aromatic dicarboxylic acid is in the range of 0.01 to 2 g, and the titanium halide is in the range of 0.1 g or more, preferably 1 g or more, per 1 g of magnesium fatty acid. Further, the halogenated hydrocarbon is used in an arbitrary ratio, but it is preferably an amount capable of forming a suspension.

At this time, the contact order and contact method of the respective raw materials forming the catalyst component are not particularly limited, but in a preferred embodiment, (1) the components (a) and (b) are suspended on the component (d). A method in which the suspension is turbid and the resulting suspension is added to the component (e) to cause a catalytic reaction, and the component (c) is allowed to coexist at any time; ), The resulting suspension is added to the component (e) in which the component (b) is allowed to coexist, and a catalytic reaction is performed, at which time the component (c) is allowed to coexist. And the component (b) is suspended in the component (d), and the resulting suspension is added to the component (e) in which the component (a) is allowed to coexist to cause a catalytic reaction. The method of making component (c) coexist can be mentioned.

As a contact condition of each raw material in the present invention, the contact of the fatty acid magnesium with the halogenated hydrocarbon is carried out usually in the presence or absence of the diester of the aromatic dicarboxylic acid from 0 ° C. to the boiling point of the halogenated hydrocarbon used. At a temperature of 100 hours or less, preferably 10 hours or less.

The contact between the suspension and the titanium halide in the present invention is carried out in the presence or absence of a diester of an aromatic dicarboxylic acid, in the temperature range from -10 ° C to the boiling point of the titanium halide used, for 10 minutes. It is preferably carried out for about 100 hours.

The composition obtained after the contact may be repeatedly contacted with a titanium halide, or may be washed with an organic solvent such as n-heptane.

The series of operations in the present invention is preferably performed in the absence of oxygen and water.

The catalyst component produced as described above is combined with the nitrogen-containing organic compound and the organoaluminum compound to form a catalyst for olefin polymerization. The organoaluminum compound used is used in a range of 1 to 1000 in molar ratio per mole of titanium atom in the catalyst component, and the nitrogen-containing organic compound is
The molar ratio per mol of the organoaluminum compound is 1 or less, preferably 0.005 to 0.5.

The polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gas or liquid state. Polymerization temperature is 200
℃ or less preferably 100 ℃ or less, the polymerization pressure is 100kg / c
m ² · G or less, preferably 50 kg / cm ² · G or less.

Olefins homopolymerized or copolymerized using the catalyst produced by the method of the present invention are ethylene, propylene,
1-butene and the like.

〔Example〕

 The present invention will be specifically described below with reference to examples.

Example 1 [Preparation of catalyst component] Nitrogen gas was sufficiently replaced, and a capacity of 200 m equipped with a stirrer
A 10-liter round-bottomed flask was charged with 10 g of magnesium stearate, 0.5 g of dipropyl phthalate and 25 ml of methylene chloride to give a suspension, and the mixture was stirred under reflux for 1 hour. This suspension was then pumped into 100 ml of room temperature TiCl ₄ in a 300 ml round bottom flask equipped with a stirrer, heated to 110 ° C. and reacted for 2 hours with stirring. After completion of the reaction, it was washed 10 times with 100 ml of n-heptane at 40 ° C., and 100 ml of TiCl ₄ was newly added to it 11
The reaction was carried out at 0 ° C. for 2 hours with stirring.

After the reaction was completed, it was cooled to 40 ° C, and then 100 ml of n-heptane
The washing was repeated, and when chlorine was no longer detected in the washing liquid, the washing was completed and it was regarded as a contact component. At this time, the solid content of the catalyst component was separated and the titanium content of the solid content was measured to be 2.98% by weight.

[Overlap]

700 ml of n-heptane was charged into an autoclave with an internal volume of 2.0, which was completely replaced with nitrogen gas, and 301 mg of triethylaluminum was added while maintaining a nitrogen gas atmosphere.
175 mg of o-anisidine, and then 0.2 mg of the above catalyst component as titanium atoms were charged. Then add 300 ml of hydrogen gas.
6kg / cm ² while heating to 70 ℃ and introducing propylene gas
Polymerization was carried out for 4 hours while maintaining the pressure of G. After the completion of the polymerization, the solid polymer obtained was separated, heated to 80 ° C. and dried under reduced pressure to obtain 186 g of a solid polymer. Meanwhile, the liquid was condensed to obtain 6.7 g of a polymer. The MI of the solid polymer is
It was 15.

Example 2 When the same experiment as in Example 1 was carried out with the polymerization time being 6 hours, 271 g of a solid polymer was obtained. The MI of the solid polymer was 18. The polymer obtained by condensing the liquid is
It was 9.7 g.

Example 3 The same experiment as in Example 1 was conducted except that 130 mg of o-anisidine was used. As a result, 208 g of a solid polymer was obtained. The MI of the solid polymer was 16. The amount of the polymer obtained by condensing the liquid was 11.5 g.

〔The invention's effect〕

When the olefins are polymerized using the catalyst obtained according to the present invention, it is obvious that the polymer produced has extremely high stereoregulatory property, and the catalyst is very highly active. The catalyst residue can be suppressed to an extremely low level, and since the amount of residual chlorine is very small, the effect of chlorine on the produced polymer can be reduced to the extent that no deashing step is required.

Chlorine contained in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, and also causes deterioration of the produced polymer itself, yellowing, etc. Has a very important meaning to those skilled in the art.

Further, the feature of the present invention is that not only the big problem of the odor of the produced polymer is solved by not using the aromatic carboxylic acid ester during the polymerization, but the activity per unit time of the catalyst is It is an object of the present invention to solve the essential drawback of so-called highly active supported catalysts, which is significantly reduced with the increase of the above, and to provide a catalyst that can be practically applied not only to homopolymerization but also to copolymerization.

In addition, in the industrial production of olefin polymers, coexistence of hydrogen at the time of polymerization is generally considered from the viewpoint of MI control and the like, but a catalyst using a catalyst component having the above magnesium chloride as a carrier is hydrogen. In the coexistence, it had a drawback that activity and stereoregularity were significantly reduced. However, when olefins are polymerized in the presence of hydrogen using the catalyst obtained according to the present invention, the MI of the produced polymer is
The activity and stereoregularity are hardly deteriorated even when the value is extremely high, and such an effect brings an extremely great benefit to those skilled in the art.

[Brief description of drawings]

FIG. 1 is a flow chart for explaining the present invention.

Claims (1)

[Claims] 1. A) (a) fatty acid magnesium, (b)
A catalyst component obtained by contacting a diester of an aromatic dicarboxylic acid, (c) a halogenated hydrocarbon and (d) a titanium halide represented by the general formula TiX ₄ (where X is a halogen element), (B ) General formula A catalyst for olefin polymerization, comprising a nitrogen-containing organic compound represented by the formula (wherein R is an alkyl group or an alkoxy group) and (C) an organoaluminum compound.