JPH078888B2 - 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. More specifically, dialkoxymagnesium is suspended in a liquid halogenated hydrocarbon, and then contacted with titanium halide to dry the resulting composition, and then contacted with the titanium halide again. A catalyst component obtained by contacting with a diester of an aromatic dicarboxylic acid at any time, the general formula SiRm (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. ) It relates to a catalyst for olefin polymerization which comprises a silicon compound and an organoaluminum compound.

[Prior Art] Conventionally, a combination of a solid titanium halide and an organoaluminum compound has been well known and widely used as a catalyst for olefin polymerization, but a catalyst component and a polymer per titanium in the catalyst component are widely used. However, the so-called deashing step for removing the catalyst residue was not possible because of the low yield (hereinafter referred to as the catalyst component and the polymerization activity per titanium in the catalyst component). 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 tendency, a transition metal compound such as titanium halide, which is an active ingredient, is supported on a carrier substance such as magnesium chloride, and when subjected to the polymerization of olefins, the polymerization activity per titanium in the catalyst component is dramatically increased. There are many proposals that have been raised.

For example, in Japanese Unexamined Patent Publication (Kokai) No. 50-126590, a carrier material, magnesium chloride, is brought into contact with an aromatic carboxylic acid ester by mechanical means, and titanium tetrahalide is added to the obtained solid composition in a liquid phase. A method of contacting to obtain a catalyst component is disclosed.

[Problems to be solved by the invention]

However, the chlorine contained in magnesium chloride not only causes the deterioration and yellowing of the produced polymer like the halogen element in titanium halide, but also causes the corrosion of the equipment used in the steps such as granulation and molding. Therefore, a high activity is required so that the effect of chlorine can be practically neglected.However, in the catalyst using the catalyst component using magnesium chloride as a carrier substance disclosed in the above publications, etc., It has not been possible to obtain sufficient performance up to.

Further, when using a catalyst having the above-mentioned magnesium chloride as a carrier, or a highly active supported catalyst which has been recently proposed variously, the polymerization activity per unit time is high at the initial stage of the polymerization, but the decrease with the passage of the polymerization time is large. However, in addition to the problems in the process operation, it was almost impossible to use it in practice when it is necessary to prolong the polymerization time such as block copolymerization.

The present inventors have achieved the present invention as a result of earnest research in order to solve the problems left over in the prior art and to further improve the quality of the polymer produced.

[Means for solving problems]

That is, the feature of the present invention is that (A) (a) dialkoxymagnesium is suspended in (b) liquid halogenated hydrocarbon, and then (c) general formula TiX ₄ (X Is a halogen element.) A composition obtained by contacting a titanium halide represented by the formula (hereinafter, may be simply referred to as “titanium halide”) is dried and then contacted with the titanium halide again. At any time, (d) a catalyst component obtained by contacting with a diester of an aromatic dicarboxylic acid; (B) a general formula SiRm (OR ') _4- m (wherein R is hydrogen, an alkyl group or an aryl group). And R ′ is an alkyl group or an aryl group, and m is 0 ≦ m ≦ 4) (hereinafter sometimes simply referred to as a silicon compound) and (C) an organoaluminum compound. It is to provide a olefin compound catalyst for polymerization.

Examples of dialkoxy magnesium used in the present invention include diethoxy magnesium, dibutoxy magnesium, diphenoxy magnesium, dipropoxy magnesium, di-sec-butoxy magnesium, di-tert-butoxy magnesium, and diisopropoxy magnesium. To be

Examples of the halogenated hydrocarbon used in the present invention include propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane, trichloroethylene, methylene chloride, dichloropropane, dichlorobenzene and trichloroethane. , Carbon tetrachloride, chloroform, methylene chloride and the like.

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

Examples of the titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element) used in the present invention include TiCl ₄ , TiBr ₄ , TiI _4, etc., among which TiCl ₄ is preferable.

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

Examples of the organoaluminum compound used in the present invention include trialkylaluminums, dialkylaluminum halides, alkylaluminum dihalides, and mixtures thereof.

The use ratio of each component in the present invention is optional as long as it does not adversely affect the performance of the catalyst to be produced, and is not particularly limited, but usually 1 g of dialkoxymagnesium, diesters of aromatic dicarboxylic acid are 0.01 g. ~ 2g,
It is preferably in the range of 0.1 to 1 g, and the titanium halide is
It is used in an amount of 0.1 g or more, preferably 1 g or more. Further, the halogenated hydrocarbon is used in an arbitrary ratio as long as it can form a suspension.

Suspension of dialkoxymagnesium in a halogenated hydrocarbon in the present invention is carried out at a temperature usually from room temperature to a boiling point of the halogenated hydrocarbon used for 100 hours or less, preferably 10 hours or less. At this time, it is necessary that the suspension does not become a uniform solution. The contact between the suspension and the titanium halide is usually -20 ° C to the boiling point of the titanium halide used, preferably 50 ° C.
It is carried out at a temperature of ~ 120 ° C for 10 minutes to 10 hours. At this time, it is preferable to add the suspension to titanium halide.

The obtained composition is usually dried under reduced pressure or by airflow drying using an inert gas such as nitrogen or argon, but the temperature, time, etc. adversely affect the performance of the obtained catalyst component. It is optional unless otherwise specified.

Contact with the titanium halide after drying is usually from -20 ° C to the boiling point of the titanium halide used, preferably 50
It is carried out at a temperature of ℃ to 120 ℃ for 10 minutes to 10 hours.
The diester of aromatic dicarboxylic acid can be used at any of the above points.

The contacting means of each component in the present invention is not particularly limited as long as each component can be sufficiently contacted, but it is usually carried out by stirring using a container equipped with a stirrer.

In the present invention, it is also possible to wash with an organic solvent such as n-heptane after the contact with the titanium halide.

The organoaluminum compound used in the present invention is used in a molar ratio of 1 to 1000 per titanium atom in the catalyst component, and the silicon compound is used in a molar ratio of 0.01 to 0.5 per mol of the organoaluminum compound.

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, 4-methyl-1-pentene and the like.

[Effect of the Invention] According to the present invention, the catalyst performance can be dramatically improved, and as a result, the amount of chlorine in the produced polymer can be neglected together with the decrease in the amount of chlorine contained in the catalyst component. It was possible to reduce to.

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 using magnesium chloride as a catalyst coexists with hydrogen. Below, it had the disadvantage that activity and stereoregularity were significantly reduced. However, when olefins are polymerized using the catalyst obtained according to the present invention, even if hydrogen is coexisted during the polymerization, the activity and the stereoregularity are hardly reduced, and such an effect is obtained. It is extremely profitable to the trader.

In addition to the effects of the present invention, not using the aromatic carboxylic acid ester during the polymerization not only solves the conventional big problem of the odor of the produced polymer, but also the activity of the catalyst per unit time is greatly improved. It is an object of the present invention to solve the essential drawbacks of so-called highly active supported catalysts, which can be substantially applied to not only homopolymerization but also copolymerization.

Further, in the drying step included in the production step of the catalyst component, the particle size of the catalyst component produced by changing the degree, the method, etc., and thus the polymer obtained by using the catalyst component of the present invention The granularity of can also be controlled. This is a great advantage as a catalyst used industrially.

〔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 1-liter round bottom flask was charged with 5 g of diethoxymagnesium, 1.5 ml of propylphthalate and 50 ml of methylene chloride to give a suspension, and the mixture was stirred under reflux for 1 hour. Then, this suspension was pumped into 200 ml of room temperature TiCl ₄ in a 500 ml round-bottomed flask equipped with a stirrer, heated to 90 ° C. and reacted for 2 hours while stirring. After the reaction, n-heptane 200m at 40 ℃
The solid portion was separated by washing 10 times with l, and the solid portion was washed with 0.1
After drying under reduced pressure up to the torr vacuum level, new TiCl
₄ 200 ml was added and reacted at 120 ° C. for 2 hours with stirring. After completion of the reaction, 200 ml of n-heptane at 40 ° C was washed 10 times to obtain a catalyst component. At this time, the solid-liquid in the catalyst component was separated, and the titanium content of the solid was measured and found to be 2.88% 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, 64 mg of phenyltriethoxysilane were charged while maintaining a nitrogen gas atmosphere, and then the catalyst component was titanium. 0.2 mg was charged as an atom. Then 180 ml of hydrogen gas
6k while charging propylene gas and raising the temperature to 70 ° C and introducing propylene gas
Polymerization was carried out for 4 hours while maintaining the pressure of g / cm ² · G.
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 liquid is concentrated and the amount of the polymer dissolved in the polymerization catalyst is (A), and the amount of the solid polymer is (B). The obtained solid polymer was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount is designated as (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. Residual chlorine in the produced polymer is represented by (G) and MI of the produced polymer is represented by (H). The results obtained are the first
As shown in the table.

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.

Example 3 An experiment was performed in the same manner as in Example 1 except that the vacuum drying was performed up to a vacuum degree of 0.5 torr. The titanium content in the solid content at this time was 3.01% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Example 4 1.8 ml of butyl phthalate instead of propyl phthalate
An experiment was conducted in the same manner as in Example 1 except that the above was used. The titanium content in the solid content at this time was 2.72% by weight. 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 suspension of (A) (a) dialkoxymagnesium in (b) liquid halogenated hydrocarbon, after which (c) a general formula TiX ₄ (wherein X is a halogen element). After contacting the titanium halide represented by the formula (1) and drying the resulting composition, it is again contacted with the titanium halide, at which time (d) a diester of an aromatic dicarboxylic acid is contacted. The resulting catalyst component; (B) General formula SiRm (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.) A catalyst for olefin polymerization, which comprises a silicon compound represented by the formula (4) and (C) an organoaluminum compound.