JPH07664B2 - Catalyst for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a stereoregular polymer having a highly active activity and an ordered particle size distribution in an extremely high yield when subjected to the polymerization of olefins. The present invention relates to a high-performance catalyst that can be obtained, more specifically, heating a solid composition obtained by contacting dialkoxy magnesium, diester of aromatic dicarboxylic acid, halogenated hydrocarbon and titanium halide in the presence of halogenated hydrocarbon. The present invention relates to an olefin polymerization catalyst comprising a olefin polymerization catalyst component obtained by treatment, a silicon compound and an organoaluminum compound.

[Conventional technology]

Conventionally, as a catalyst for olefin polymerization having high activity, 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 per titanium (hereinafter referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) was 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 recovering device or a regenerating device for them is indispensable, and there are many resources, energy, and other incidental problems, and those skilled in the art can quickly solve the problem. This is an important issue that is desired. 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 trend, when a transition metal compound such as titanium halide which is an active ingredient is supported on a carrier substance such as magnesium chloride and 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 the drawback that it adversely affects the polymer produced as well as the halogen element in titanium halides, and 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.

SUMMARY OF THE INVENTION The inventors of the present invention aimed 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.
In 0454, a method for producing a catalyst component for polymerization of olefins was proposed, and the intended 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 organic aluminum 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 M-O-R are prepared.
A method of using it for the polymerization of olefins in combination with a compound having a group 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 above, very complicated operations are required, and it cannot be said that a practically sufficient one is obtained in terms of performance and sustainability of activity.

Further, in an industrial polymerization apparatus, it may be necessary to supply the catalyst to a high temperature polymerization tank, but in the case of the conventional supported catalyst, the performance is particularly large, especially the activity, stereoregularity, and bulk specific gravity. Is known to decrease. This is a big problem especially in the so-called continuous slurry polymerization method using an organic solvent, and there has been a strong demand in the art for its improvement.

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, a feature of the present invention is that (A) (a) dialkoxymagnesium, (b) diester of aromatic dicarboxylic acid, (c) halogenated hydrocarbon, and (d) general formula TiX ₄ (X in the formula: Is a halogen element.) A solid obtained by contacting a titanium halide (hereinafter simply referred to as “titanium halide”) represented by the formula (d) with the titanium halide. A catalyst component obtained by heat-treating the composition in the presence of (e) a halogenated hydrocarbon (which may be the same as or different from the component (c)); (B) a general formula SiR _m ( OR ') _4-m (wherein R is hydrogen, an alkyl group or an aryl group, R'is an alkyl group or an aryl group, and m is 0≤m≤4) , Simply silicon compounds There);. And (C) is to provide a olefin compound polymerization catalyst consisting of an organoaluminum compound.

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 aromatic dicarboxylic acid diester used in the present invention is preferably a phthalic acid diester, for example, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl. Examples thereof include 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.

The titanium halide used in the present invention is
TiCl ₄ , TiBr ₄ , TiI _{4 and the} like can be mentioned, but TiCl ₄ is particularly preferable.

As the silicon compound used in the present invention,
Examples thereof include phenylalkoxysilane and alkylalkoxysilane. Further examples of phenylalkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. Examples of the alkylalkoxysilane include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriisopropoxysilane.

When obtaining the solid composition of the present invention, the use ratio of each raw material and the contact conditions are optional, and are not particularly limited, as long as they do not adversely affect the performance of the produced catalyst component. With respect to 1 g of dialkoxy magnesium, the diester of aromatic dicarboxylic acid is in the range of 0.01 to 2 g, preferably 0.1 to 1 g, and the titanium halide is
The range is 0.1 g or more, preferably 1 g or more. Further, the halogenated hydrocarbon is used in an arbitrary ratio, but is preferably an amount capable of forming a suspension.

Further, the contact of each raw material is usually carried out at a temperature from 0 ° C. to the boiling point of the titanium halide used for 100 hours or less, preferably 10 hours or less.

At this time, the order and method of contacting each raw material are not particularly limited, and any appropriate one can be selected.

The composition obtained by the contact is further contacted with a titanium halide to form a solid composition. The contact conditions at this time may be the same as those at the contact, and before and after the contact. It is also possible to wash with an organic solvent such as n-heptane.

The heat treatment of the solid composition thus obtained is carried out in the presence of 0.1 g or more of halogenated hydrocarbon per 1 g of the solid composition, usually at a temperature of 30 ° C. or higher for 10 hours or less, preferably 5 hours. The following is done.

At this time, the heat treatment can be performed under pressure or reduced pressure.

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

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.

〔The invention's effect〕

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

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.

Conventionally, in industrial olefin polymer production, it has been generally said that hydrogen is allowed to coexist at the time of polymerization from the viewpoint of MI control and the like. Below, it had the disadvantage 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.

Further, in an industrial polymerization apparatus, it may be necessary to supply the catalyst to a high temperature polymerization tank, but in the case of a conventional supported catalyst, the performance, particularly activity, stereoregularity, bulk It is known that specific gravity decreases. This is a big problem especially in the so-called continuous slurry polymerization method using an organic solvent, and there has been a strong demand in the art for its improvement, but the catalyst according to the present invention sufficiently solves this problem.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 <Preparation of catalyst component> 200 m fully replaced with nitrogen gas and equipped with a stirrer
A 1-liter round-bottomed flask was charged with 5 g of diethoxymagnesium, 1.6 g of dibutyl phthalate and 25 ml of o-dichlorobenzene to give a suspension, and the mixture was stirred under reflux for 1 hour. This suspension was then pumped into 200 ml of room temperature TiCl ₄ in a 500 ml round bottom flask equipped with a stirrer and heated to 120 ° C.
After reacting while stirring for an hour, the supernatant is removed and fresh
200 ml of TiCl ₄ was added and reacted at 120 ° C. for 2 hours with stirring. After completion of the reaction, the product was washed 10 times with 200 ml of n-heptane at 40 ° C. and then dried under reduced pressure to obtain a solid composition. At this time, the titanium content of the solid composition was 2.67%. Next, 3 g of the solid composition was completely replaced with nitrogen gas, and the internal volume was 200 m.
Transfer to a round-bottomed flask equipped with a stirrer of l, add 30 ml of n-dichlorobenzene and heat at 30 ° C for 30 minutes, then
The catalyst component was washed 5 times with 100 ml of n-heptane at 0 ° C.

<Polymerization> 700 ml of n-heptane was charged into an autoclave with an internal volume of 2.0 l, which was completely replaced with nitrogen gas, and 301 mg of triethylaluminum and 64 mg of phenyltriethoxysilane were charged while maintaining a nitrogen gas atmosphere. did. 80 ℃ thereafter
The temperature was raised to 10.0 mg of the catalyst component and 120 ml of hydrogen gas.
Was charged, and the polymerization was carried out for 4 hours while maintaining the pressure of 6 kg / cm ² · G while introducing propylene gas. After completion of the polymerization, the solid polymer obtained was separated, heated to 80 ° C. and dried under reduced pressure. On the other hand, the amount of the polymer dissolved in the polymerization solvent by condensing the liquid is (A), and the amount of the solid polymer is (B). The obtained solid polymer was extracted with boiling n-heptane for 6 hours, and
A polymer insoluble in heptane is obtained, this amount being (C).

The polymerization activity (D) per catalyst component is calculated by the formula Express with.

Further, the yield (E) of the crystalline polymer is calculated by the formula The yield (F) of all crystalline polymer is expressed by I asked more. The residual chlorine in the produced polymer is represented by (G), the MI of the produced polymer is represented by (H), and the bulk specific gravity is represented by (I). The results obtained are as shown in Table 1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 6 hours. The results obtained are as shown in Table 1.

Comparative Example 1 The solid composition obtained in Example 1 was used as a catalyst component without heat treatment. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. (A) (a) dialkoxy magnesium,
A solid composition obtained by contacting (b) 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). (D) The titanium halide is brought into contact with the product to obtain a solid composition (e).
A catalyst component obtained by heat treatment in the presence of a halogenated hydrocarbon (which may be the same as or different from the component (c)); (B) a general formula SiRm (OR ') 4-m (in the formula) R is hydrogen, an alkyl group or an aryl group, R'is an alkyl group or an aryl group, and m is 0≤m≤4); and (C) an organoaluminum compound. A catalyst for olefin polymerization, which is characterized by: