JPH0655784B2 - Olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is a high-performance catalyst that acts highly when subjected to the polymerization of olefins and that can obtain a stereoregular polymer in high yield. More specifically, from a catalyst component for olefin polymerization, a piperidine derivative and an organoaluminum compound obtained by bringing fatty acid magnesium, dialkoxy magnesium, aromatic dicarboxylic acid diester, halogenated hydrocarbon and titanium halide into contact with each other. The present invention relates to a catalyst for olefin polymerization.

[Conventional technology]

Conventionally, as a catalyst for polymerization of olefins, 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 were many energy and other incidental problems, and it was an important issue for those skilled in the art to solve 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 carrier 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. 57-200
In 454, a method for producing a catalyst component for olefin polymerization was proposed, and the intended purpose was achieved. Further, when the polymerization of olefins, particularly stereoregular polymerization of propylene, 1-butene, etc. 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 has become 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 polymerization is high, 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 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. Although a method used for the polymerization of olefins in combination with, etc. is shown, 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 feature of the present invention is that (A) (a) fatty acid magnesium, (b) dialkoxy magnesium, (c) aromatic dicarboxylic acid diester, (d) halogenated hydrocarbon and (e) general formula TiX. _{4 A} composition obtained by contacting a titanium halide represented by the formula (where X is a halogen element) (hereinafter may be simply referred to as titanium halide) with the titanium halide. Another object of the present invention is to provide a catalyst for olefin polymerization comprising the above catalyst component (B) piperidine derivative (C) organoaluminum compound.

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.

As dialkoxy magnesium used in the present invention, diethoxy magnesium, dibutoxy magnesium, diphenoxy magnesium, dipropoxy magnesium, di-sec-butoxy magnesium, di-tert-
Examples thereof include butoxy magnesium and diisopropoxy magnesium, and among them, diethoxy magnesium and dipropoxy magnesium are preferable.

The fatty acid magnesium and dialkoxymagnesium are 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 phthalic acid or terephthalic acid diester, for example, dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate,
Examples thereof include dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, 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 which 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 piperidine derivative used in the present invention is preferably a disubstituted or tetrasubstituted derivative.

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 aromatic dicarboxylic acid diester 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 based on 1 g of the total amount of the fatty acid magnesium and the dialkoxy magnesium. Also,
The halogenated hydrocarbon is used in any proportion, but is preferably an amount capable of forming a suspension.

At this time, the contact order and contact method of each raw material forming the catalyst component are not particularly limited, but in a preferred embodiment, (1) components (a) and (b) are suspended in 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; (2) the component (a) is added to the component (d) ), And the resulting suspension,
Add the component (b) to the coexisting component (e) to cause a catalytic reaction,
At that time, the component (c) is allowed to coexist at any time; and the component (b) is suspended in the component (d), and the resulting suspension is
A method may be mentioned in which (a) is added to the coexisting component (e) to cause a catalytic reaction, and the component (c) is allowed to coexist at any point in time.

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

The suspension of the present invention is contacted with a titanium halide or a titanium halide in which dialkoxy magnesium or fatty acid magnesium is coexisted, in the presence or absence of an aromatic dicarboxylic acid diester, usually-
It is preferably carried out at a temperature range from 10 ° C. to the boiling point of the titanium halide used for 10 minutes to 100 hours.

The catalyst component used in the present invention is prepared by further bringing a titanium halide into contact with the composition produced by the above contact. The contact conditions at this time may be the same as those described above. It is also possible to wash the composition and / or the catalyst component with an inert 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 piperidine derivative and the organoaluminum compound to form an olefin polymerization catalyst. The organoaluminum compound used is used in a molar ratio of 1 to 1000 per mol of titanium atom in the catalyst component, and the piperidine derivative 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 a 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.

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

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

Example 1 <Preparation of catalyst component> A capacity of 200, which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
5 g of magnesium stearate in a round bottom flask of m,
Diethoxy magnesium 5g, dipropyl phthalate 1.
5 g and 50 m of methylene chloride were charged to make a suspension, and the mixture was stirred under reflux for 1 hour. This suspension is then added to TiC at room temperature in a 500 m round bottom flask equipped with a stirrer.
It pumped into l ₄ 200 meters, and reacted with stirring for 2 hours the temperature was raised to 120 ° C.. After the reaction, n-heptane 200m at 40 ℃
It was washed 10 times with, 200 ml of TiCl ₄ was newly added, and the reaction was carried out while stirring at 120 ° C. for 2 hours.

After the reaction was completed, the mixture was cooled to 40 ° C and then n-heptane 200m
The washing was repeated, and when chlorine was not detected in the washing liquid, the washing was completed and the catalyst component was used.
At this time, the solid-liquid in the catalyst component was separated and the titanium content of the solid was measured to be 2.16% by weight.

<< Polymerization >> 700 m of n-heptane was charged into an autoclave with an agitator having an internal volume of 2.3, which was completely replaced with nitrogen gas, and 301 m of triethylaluminum was added while maintaining a nitrogen gas atmosphere.
g, 2,2,6,6-tetramethylpiperidine (74 mg), and then the catalyst component (0.2 mg) as titanium atom was charged. Then, 300 m of hydrogen gas was charged, the temperature was raised to 70 ° C., and propylene gas was introduced while maintaining a pressure of 6 kg / cm ² · G to carry out polymerization for 4 hours. Separate the solid polymer obtained after the completion of polymerization,
When heated to 80 ° C. and dried under reduced pressure, 331 g of a solid polymer was obtained. Meanwhile, the liquid was condensed to obtain 1.7 g of a polymer. The MI of the solid polymer was 18.

Example 2 When the same experiment as in Example 1 was carried out with the polymerization time being 2 hours, 193 g of a solid polymer was obtained. The MI of the solid polymer was 21. The amount of the polymer obtained by condensing the liquid was 1.0 g.

Example 3 The same experiment as in Example 1 was conducted except that 148 mg of 2,2,6,6-tetramethylpiperidine was used. As a result, 356 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 1.7 g.

〔The invention's effect〕

When olefins are polymerized using the catalyst obtained according to the present invention, the resulting polymer has extremely high stereoregularity, and the catalyst has a very high activity. Can be controlled to an extremely low level, and the effect of chlorine on the produced polymer can be reduced to such an extent that a deashing step is not required at all due to the small amount of residual chlorine.

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 at the time of polymerization, but also the activity of the catalyst per unit time is increased with the progress of the polymerization. Will be significantly reduced. It is an object of the present invention to solve the essential drawbacks of so-called highly active supported catalysts and to provide a catalyst that can be practically applied not only to homopolymerization but also to copolymerization.

Further, in 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 the above-mentioned catalyst component having magnesium chloride as a carrier is hydrogen. In the coexistence, it had a drawback that activity and stereoregularity were significantly reduced.
However, when the olefins are polymerized in the coexistence of hydrogen using the catalyst obtained by the present invention, the activity and stereoregularity are hardly decreased even when the MI of the produced polymer is extremely high. Such an effect brings extremely great benefits to those skilled in the art.

[Brief description of drawings]

FIG. 1 is a flowchart showing the catalyst manufacturing process of the present invention.

Claims (1)

[Claims] 1. A) (a) fatty acid magnesium, (b) dialkoxy magnesium, (c) aromatic dicarboxylic acid diester, (d) halogenated hydrocarbon and (e) general formula TiX.
₄ (wherein X is a halogen element), a catalyst obtained by contacting a titanium halide represented by the formula: (B) piperidine derivative and (C) ) A catalyst for olefin polymerization, comprising an organoaluminum compound.