JPS6123606A - Olefin polymerization catalyst component and catalyst - Google Patents

Abstract

PURPOSE:A catalyst which has high activity and can give a stereoregular polymer in good yield, comprising a specified catalyst component, an oxygen-containing organic compound and an organoaluminum compound. CONSTITUTION:A catalyst component is obtained by bringing 1g of the total of a magnesium salt of a fatty acid (e.g., magnesium stearate) and a dialkoxymagnesium (e.g., diethoxymagnesium), 0.01-2g of a mono- or di-ester of an aromatic dicarboxylic acid (e.g., dimethyl phthalate) and 0.1g or above titanium halide compound of the formula: TiX4 (wherein X is a halogen) and a halohydrocarbon (e.g., CCl4) into contact with each other at -10 deg.C or higher for 10min-100hr. This catalyst component is combined with an oxygen-containing organic compound of the formula (wherein R is alkyl or alkoxy) and an organoaluminum compound (e.g., triethylaluminum) to obtain a catalyst. An olefin is polymerized in the presence of said catalyst under conditions including a temperature <=200 deg.C and a pressure <=100kg/cm.G.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a high-performance catalyst component and a method for producing the catalyst that act with high activity when subjected to the polymerization of olefins and can obtain a stereoregular polymer in high yield. More specifically, a catalyst component for polymerizing olefins obtained by contacting fatty acid magnesium, dialkoxymagnesium, mono- or diester of aromatic dicarboxylic acid, halogenated hydrocarbon, and titanium halide, and the catalyst component and oxygen-containing organic compound. and a catalyst for polymerizing olefins comprising an organoaluminium compound.

Conventionally, as a catalyst for polymerizing olefins, a combination of a solid titanium halide and an organoaluminum compound as a catalyst component 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 to remove the media residue has been unavoidable. This deashing process uses a large amount of alcohol or chelating agent, so recovery or regeneration equipment is essential.
There are many energy and other related problems, and it is an important issue that those skilled in the art would like to solve as soon as possible. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity of titanium in the catalyst component and the sieving catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity of titanium in the catalyst component can be dramatically increased. There are many proposals to raise the standard.

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the formed polymer, similar to the chlorine element in titanium chlorides, and as a result, chlorine is effectively There remained unresolved issues such as the requirement for high activity so that the influence could be ignored, or the need to keep the concentration of magnesium chloride itself low.

The present inventors have developed a patent application filed in Japanese Patent Application No. 1983-1-1 with the aim of reducing the residual chlorine in the produced polymer while maintaining the polymerization activity of the catalyst component and the yield of the stereoregular polymer at a high level.
No. 200454, we proposed a method for producing a catalyst component for the polymerization of oleynes, and achieved the intended purpose. Furthermore, when polymerizing olefins, especially stereoregular polymerization of propylene, l-butene, etc., is carried out industrially, an electron-donating compound such as an aromatic carboxylic acid is usually co-existed in the polymerization system. It is essential for catalysts that use the aforementioned magnesium chloride-based catalyst component in combination with an organoaluminum compound. However, this aromatic carboxylic acid ester imparts a characteristic ester odor to the produced polymer, and its removal has become a major problem in the industry.

In addition, in so-called highly active supported catalysts, such as catalysts using catalyst components using magnesium chloride as a carrier,
Although the activity is high in the initial stage of polymerization, deactivation 1) 5 major factors causes problems in process operation, and is almost impossible to use in practical cases where longer polymerization times are required, such as in block copolymerization. Met. Should I improve point B? For example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material, and an organic aluminum compound, an organic carboxylic acid ester,
A method has been proposed in which olefins are polymerized in combination with a compound having an M-0-R group, but since an organic carboxylic acid ester is used during polymerization, the problem of odor of the resulting polymer has not been solved. Moreover, as can be seen from the examples, it requires very complicated operations, and it cannot be said that it has been obtained that is practically sufficient in terms of performance and duration of activity.

The present inventors have arrived at the present invention as a result of intensive research in order to solve the problems remaining in the prior art, and hereby propose the present invention.

That is, the features of the present invention are as follows: IA) (a) magnesium fatty acid, (b) dialkoxymagnesium, (C) mono''! or diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and ( e) General formula TiX4 (wherein X is a halogen element).

) titanium halide (hereinafter referred to as mono-nichita 7)
Sometimes called halides. ) and used in combination with (a) an oxygen-containing organic compound and (c) an organoaluminum compound; alkoxymagnesium, (C) mono- or diester of aromatic dicarboxylic acid, (d) halogenated ffhydrogen and (e
) -ff formula TiX4 (wherein X is a halogen element.

) A catalyst component obtained by contacting a titanium halide (hereinafter sometimes simply referred to as a titanium halide) represented by The present invention provides a catalyst for polymerizing olefins.

When olefins are polymerized using the catalyst obtained according to the present invention, not only the produced polymer has extremely high stereoregularity, but also the catalyst residue in the produced polymer is very high. Moreover, since the amount of residual chlorine is extremely small, the influence of chlorine on the produced polymer can be reduced to such an extent that a deashing step is not required at all.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration and yellowing of the produced polymer itself, and this has been reduced. This has extremely important meaning for those skilled in the art.

Furthermore, the present invention is characterized by not using an aromatic carboxylic acid ester during polymerization, which solves the major problem of the odor of the produced polymer, and by controlling the activity of the catalyst per unit time over the course of polymerization. The purpose is to solve the essential drawbacks of so-called high-activity supported catalysts, which are significantly reduced with the increase in activity, 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, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but the catalyst using the catalyst component with magnesium chloride as a carrier is In coexistence, the activity and stereoregularity were significantly reduced.

However, when oleynes are polymerized in the presence of hydrogen using the catalyst obtained according to the present invention, the activity and stereoregularity hardly decrease even when the MI of the resulting polymer is extremely high. , such an effect brings extremely great benefits to those skilled in the art.

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

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ec-butoxymagnesium, di-te
Examples include rt-butoxymagnesium, diisopropoxymagnesium, and the like, with jetoxymagnesium and dipropoxymagnesium being preferred.

Note that it is preferable to use the fatty acid magnesium and dialkoxymagnesium in a form with as much moisture removed as possible.

The mono- or diester of aromatic dicarboxylic acid used in the present invention is preferably a mono- or diester of phthalic acid or terephthalic acid, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate,
Examples include diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, sifthyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diynamyl phthalate, ethylpropyl phthalate, ethyl isobutyl phthalate, and ethylpropyl phthalate.

The halogenated hydrocarbon used in the present invention is preferably an aromatic or aliphatic hydrocarbon chloride that is liquid at room temperature, such as propyl chloride.

Examples include butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethyne, carbon tetrachloride, chloroform, methylene chloride, among others, propyl chloride, Dichloroethane, chloroform, carbon tetrachloride, and methylene chloride are preferred.

The titanium halide represented by the general formula TiX4 (wherein X is a halogen element) used in the present invention includes TiC24, TiBr4, TiI4, etc., and among them, TiC1a is preferred.

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

Examples of the organoaluminum compound used in the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum di-ride, and mixtures thereof. Among them, trialkylaluminum is preferred, and triethylaluminum and triisobutylaluminum are particularly preferred. preferable.

When obtaining the catalyst component of the present invention, the proportion 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, and is not particularly limited. , total ltK of normal fatty acid magnesium and dialkoxymagnesium vs. 1. , the monomer diester of aromatic dicarboxylic acid has an acid content in the range of 0.01 to 22,
The titanium halide is in the range of 012 or more, preferably 1f or more. The halogenated hydrocarbon may be used in any proportion, but preferably one capable of forming a suspension.

At this time, the order and method of contacting the raw materials forming the catalyst component are not particularly limited, but as preferred embodiments, (1) component (a) > J: and (b) to component ( d)V
cs cloudy, and the resulting suspension is added to component (e) for contact reaction, at which time component (C) is allowed to coexist; (2) component (a) is added to component (e); d), and the resulting suspension is mixed with a component (b) in which the component (b) is coexisting.
A method in which component (e) is added to component (d) to cause a contact reaction, and component (e) is allowed to coexist at some point during the reaction; and component (b) is suspended in component (d), and the resulting suspension is An example of a method is to add (a) to component (e) and cause a contact reaction, and at some point during the reaction, component (c) is allowed to coexist.

As the contact conditions for each raw material in the present invention, the contact of fatty acid magnesium and/or dialkoxymagnesium with the hydrogenated hydrocarbon is as follows: □゛In the presence or absence of mono- or diester of aromatic dicarboxylic acid The reaction is usually carried out at a temperature from 0° C. to the boiling point of the halogenated hydrocarbon used for up to 100 hours, preferably up to 10 hours.

In the present invention, the suspension is brought into contact with a titanium logide or a titanium logide in which dialkoxymagnesium or fatty acid magnesium coexists, usually in the presence or absence of a mono- or diester of an aromatic dicarboxylic acid. It is preferable to conduct the reaction at a temperature ranging from 10° C. to the boiling point of the titanium logefide used for 10 minutes to 100 hours.

It is also possible to contact the composition obtained after the above-mentioned contact with a titanium halide, and it is also possible to wash it using an organic solvent such as n-hebutane.

These series of operations in the present invention are preferably performed in the absence of oxygen, moisture, and the like.

The catalyst component produced as described above is combined with the oxygen-containing organic compound and organoaluminum compound to form a catalyst for polymerizing olefins. The organoaluminum compound used has a smol ratio of titanium atoms in the catalyst component in the range of 1 to 1000, and the oxygen-containing organic compound has a smol ratio of 1 or less, preferably 0. It is used in the range of .005 to 0.5.

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. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00 ky/crl-a or less, preferably 504 pieces/G
It is as follows.

The olefins to be homopolymerized or copolymerized using the catalyst produced by the method of the present invention include ethylene, propylene,
1-butene, etc.

The present invention will be specifically explained below using examples.

Example 1 [Preparation of catalyst component] A container Ji2 sufficiently purged with nitrogen gas and equipped with a stirrer
Magnesium stearate 5f in 00- round bottom flask
, 5f of jetoxymagnesium, 1.5F of dipropylphthalate and 5o of methylene chloride were charged to form a suspension, and the mixture was stirred under reflux for 1 hour.

This suspension was then transferred to a container with a capacity of 500 m/m equipped with a stirrer.
The mixture was pumped into TiCt4200 at room temperature in a round bottom flask, heated to 120°C and stirred for 2 hours before reacting. After the reaction was completed, it was washed 10 times with n-hebutane 200- at 40°C, and freshly added T+C14200- and heated at 120'C.
The mixture was reacted with stirring for 2 hours.

After the reaction was completed, it was cooled to 40°C, and then 20% of n-hebutane was added.
Washing at 0 mK was repeated, and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was used. At this time, when the solid and liquid in the catalyst component was separated and the titanium content of the solid was measured, it was found to be 2.16% by weight.

[Overlapping]

Contents completely replaced with nitrogen gas 2. Into an OL autoclave equipped with a stirrer, 700 g of n-hebutane was charged, and while maintaining a nitrogen gas atmosphere, 3011 Iv of triethylaluminum, 71 Iv of o-7 nisaldehyde, and then 0.00 g of titanium atoms were added to the catalyst components. 2 # charged. Thereafter, 300 °C of hydrogen gas was charged, the temperature was raised to 70°C, and while propylene gas was introduced, a pressure of 6 Jc'i/al·a was maintained, and polymerization was carried out for 4 hours. After completion of the polymerization, the obtained solid polymer was separated, heated to 80° C., and dried under reduced pressure to obtain a solid polymer of 1962.

On the other hand, liquid f was condensed to obtain a polymer of 6.91. Moreover, the MI of the solid polymer was 12.

Example 2 An experiment similar to Example 1 was conducted with the polymerization time being 6 hours, and a solid polymer of 278f was obtained.

Moreover, the MI of the solid polymer was 21. The amount of polymer obtained by condensing the r liquid was 9.5 tons.

Example 3 Example 1 except that 0-anisaldehyde was used at 143■
A similar experiment was conducted. As a result, 1782 solid polymers were obtained. The MI of the solid polymer was 11. Moreover, the amount of polymer obtained by condensing the r liquid was 5.7 tons.

Claims (2)

[Claims] (1) (A) (a) fatty acid magnesium, (b) dialkoxymagnesium, (c) mono- or diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon and (
e) Obtained by contacting titanium halide represented by the general formula TiX_4 (in the formula, or an alkoxy group) (hereinafter simply referred to as an oxygen-containing organic compound) and (C) an organoaluminum compound. (2) (A) (a) fatty acid magnesium, (b) dialkoxymagnesium, (c) mono- or diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon and (
e) Catalyst component obtained by contacting a titanium halide represented by the general formula TiX_4 (wherein X is a halogen element); Polymerization of olefins consisting of (B) an oxygen-containing organic compound and (C) an organoaluminum compound Catalyst for use.