JPS60161404A - Catalytic component for polymerizing olefin - Google Patents

Abstract

PURPOSE:The titled catalytic component providing a high stereoregular polymer, having a little reduction in catalytic activity with progress of polymerization, obtained by bringing an Mg salt of fatty acid into contact with an aromatic dicarboxylic acid ester, a halogenated hydrocarbon, and titanium chloride. CONSTITUTION:(A) A magnesium salt of fatty acid (e.g., magnesium stearate, etc.) is brought into contact with (B) an aromatic dicarboxylic acid mono- or diester (e.g., dibutyl phthalate, etc.), (C) a halogenated hydrocarbon (e.g., methylene chloride, etc.), and (D) a titanium halide (e.g., titanium trichloride, etc.) shown by the formula TiX4 (X is halogen), to give the desired catalytic component. This component is blended with an organometallic compound such as triethyl aluminum, etc., and an olefin is polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high-performance catalyst component that acts with high activity when subjected to the polymerization of olefins and is capable of obtaining stereoregular polymers in high yield. This invention relates to a catalyst component for polymerizing olefins obtained by contacting magnesium fatty acids, mono- and diesters of aromatic dicarboxylic acids, halogenated hydrocarbons, and titanium halides.

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 catalyst residues has been unavoidable. Since the demineralization process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment is essential, and resources,
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 step, many studies have been made and proposals have been made to increase the polymerization activity per titanium in the catalyst component, especially in the catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium chlorides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity per 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 therefore There remained unresolved issues such as the requirement for high activity so that the influence of superchlorine can 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, a method for producing a catalyst component for polymerizing olefins was proposed, and the intended purpose has been achieved.

However, when using the catalyst component using magnesium chloride as a carrier, or the catalyst component obtained in the patent application No. 57-200454, the polymerization activity per unit time is high at the initial stage of polymerization, but as the polymerization time elapses. The decrease was large, causing problems in process operation, and it was almost impossible to use it practically in cases where a longer polymerization time was required, such as in block copolymerization.

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: (a) magnesium fatty acid, (b) mono- and diester of aromatic dicarboxylic acid, (C) halogenated hydrocarbon,
and (d) providing a catalyst component for polymerizing olefins obtained by contacting a titanium halide (hereinafter sometimes simply referred to as titanium halide) represented by the general formula T1X4 (wherein X is a halogen element). It's there.

When olefins are polymerized using the catalyst component obtained by the present invention, the resulting polymer not only has extremely high stereoregularity but also has extremely high activity, so that catalyst residues in the resulting polymer are 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. has extremely important meaning for those skilled in the art.

Furthermore, the present invention is characterized by providing a catalyst that solves the essential drawback of so-called highly active supported catalysts, in which the activity of the catalyst components per unit time decreases significantly as the polymerization progresses. It's there.

In addition, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but the catalyst component using magnesium chloride as a carrier does not become active in the coexistence of hydrogen. It also had the disadvantage that the stereoregularity was significantly reduced. but,
When olefins are polymerized in the presence of hydrogen using the catalyst component obtained according to the present invention, the MI of the produced polymer is
The activity and stereoregularity hardly decrease even when the ratio is extremely high, and such an effect is of great benefit to those skilled in the art.

The fatty acid magnesium used in the present invention is preferably saturated fatty acid magnesium, and magnesium stearate and magnesium octoate are preferably used.The aromatic dicarboxylic acid mono- and diesters used in the present invention are preferably phthalic acid or terephthalic acid mono- and diesters. , for example, dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl imbutyl phthalate, ethyl Examples include propyl phthalate.

The halogenated hydrocarbons used in the present invention are preferably chlorides of aromatic or aliphatic hydrocarbons that are liquid at room temperature, such as propyl chloride, butyl chloride,
Butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, etc., among which propyl chloride, dichloroethane, chloroform , carbon tetrachloride, and methylene chloride are preferred.

The titanium halide represented by the general formula T1X4 (wherein X is a halogen element) used in the present invention includes TiBr4+ TiBr4+ TiI4, among which Tict is preferred.

When obtaining the catalyst component of the present invention, the proportion of each raw material constituting the catalyst component is arbitrary, and is not particularly limited, as long as it does not adversely affect the performance of the catalyst component to be produced. , mono- and diesters of aromatic dicarboxylic acids are 001-2 for normal fatty acid magnesium 1f.
2, preferably in the range of 0.1 to 1 f, titanium
Is rogenide 0.1? The above range is preferably 1 or more. Further, the halogenated hydrocarbon can be used in any proportion, but it is preferably in an amount that can form a suspension.

At this time, the order and method of contacting the raw materials forming the catalyst component are not particularly limited, but as a preferred embodiment, component (a) is suspended in component (Q), and the suspension obtained is suspended in component (Q). An example of a method is to add the suspension to component (d) and cause a contact reaction, and at some point during the reaction, component (b) is allowed to coexist.

Regarding the contact conditions for each raw material in the present invention, when fatty acid magnesium is suspended in a halogenated hydrocarbon, the halogenated hydrocarbon used in the presence or absence of mono- and gestyl aromatic dicarboxylic acids is usually It is preferable to maintain suspension at a temperature up to the boiling point for up to 100 hours, preferably up to 10 hours.

In the present invention, the suspension and the titanium halide are brought into contact in the presence or absence of mono- and diesters of aromatic dicarboxylic acids, usually at a temperature range from -10°C to the boiling point of the titanium halide used, 10 minutes to 10
It is preferable to carry out the test for 0 hours.

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

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

The catalyst component produced as described above is combined with an organoaluminum compound to form a catalyst for polymerizing olefins. The organoaluminum compound used is used in a molar ratio of 1 to 1000 per mole of titanium atoms in the catalyst component. Also, during polymerization, tertiary substances such as electron-donating substances may be added.
It is not prohibited to use additional components.

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
It is below 00 Ky/en·G, preferably below 50 xf,/en·G.

Olefins to be homopolymerized or copolymerized using the catalyst component of the present invention include ethylene, propylene, 1-butene, and the like.

The present invention will be specifically explained below using Examples and Comparative Examples.

Example 1 [Preparation of catalyst components] A 20-volume tank sufficiently purged with nitrogen gas and equipped with a stirrer
Magnesium stearate 102 in a round bottom flask
, dibutyl phthalate 1.39 and methylene chloride 25
- was charged to form a suspension, and the mixture was stirred under reflux for 1 hour.

This suspension was then pumped into a T+C14200 at room temperature in a 500-capacity round bottom flask equipped with a stirrer.
The temperature was raised to 0° C., and the mixture was reacted with stirring for 2 hours. After the reaction was completed, the mixture was washed 10 times with 200 m of n-hebutane at 40°C, and TiC1<200- was added again, and the mixture was reacted at 70°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then 20% of hebutane was added.
Washing with 0- was repeatedly performed, 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 in the solid was measured, it was found to be 3.16% by weight.

[Overlapping]

Internal volume completely replaced with nitrogen gas2. A total of 700 m of n-hebutane was charged into an autoclave equipped with a stirrer, and while maintaining a nitrogen gas atmosphere, 301 cm of triethylaluminum, 32 cm of phenyltriethoxysilane, and then 0.2 cm of the catalyst component as a titanium atom were charged. I entered. Thereafter, 300 m of hydrogen gas was charged, the temperature was raised to 7 (1), and while propylene gas was introduced, polymerization was carried out for 4 hours while maintaining a pressure of 6 Ky/cd-a. The coalesced liquid was separated into r parts, heated to ℃ and dried under reduced pressure.Meanwhile, the r liquid was condensed to calculate the amount of polymer dissolved in the polymerization solvent (4
) and the amount of solid polymer is Φ). Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as C).

The polymerization activity per catalyst component (0) was expressed by the formula and the yield (2) of the crystalline polymer was expressed by the formula, and the yield (2) of the total crystalline polymer was determined from the formula. In addition, the residual chlorine in the produced polymer is G), and the MI of the produced polymer is 0.
It is expressed as The results obtained are shown in Table 1.

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

Example 3 A catalyst component was prepared in the same manner as in Example 1 except that 1,2-dichloroethane was used instead of methylene chloride. Incidentally, the titanium content of the solid fraction at this time was 303% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 4 A catalyst component was prepared in the same manner as in Example 1 except that the reaction temperature with TiC4 was 65°C. Incidentally, the titanium content of the solid fraction at this time was 3.20% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 5 Example 1 except that 1.39 dipropyl phthalate was used.
An experiment was conducted in the same manner. Note that the titanium content of the solid fraction at this time was 327% by weight.

During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1.

Comparative Example 1 [Preparation of catalyst component] MgCl2100 f/ and ethyl benzoate 3152 were pulverized for 18 hours under a nitrogen gas atmosphere. 100f of the hindlimb crushed composition was taken out, and the internal volume was reduced to 200f under a nitrogen gas atmosphere.
The mixture was placed in a 0-glass container, TICt4500- was added thereto, and the reaction was stirred at 65°C for 2 hours. After completion of reaction 4
The mixture was cooled to 0°C, left to stand, and the supernatant liquid was removed by decantation. Next, washing with 1000 m# of n-hebutane was repeated, and when chlorine was no longer detected in the washing liquid, the washing was completed and the catalyst component was used.

At this time, the solid and liquid in the catalyst component was separated and the titanium content of the solid component was measured and found to be 1.28% by weight.

[Overlapping]

During polymerization, the catalyst component has a titanium atom of 1.0
(2) The procedure was carried out in the same manner as in Example 1, except that the following was used. The results obtained are shown in Table 1.

Comparative Example 2 [Preparation of Catalyst Component] A 20-volume reactor sufficiently purged with nitrogen gas and equipped with a stirrer.
Magnesium stearate 5f in a 0- round bottom flask,
Jetoxymagnesium 5f, ethyl benzoate 20 and methylene chloride 5o were charged to form a suspension, and the mixture was stirred under reflux for 1 hour. This suspension was then transferred to a Tict4 at room temperature in a 500-capacity round bottom flask equipped with a stirrer.
The mixture was pumped into a 200° C., heated to 90° C., and reacted with stirring for 2 hours. After the reaction is complete, add 200 ml of n-heptane at 40°C.
Wash with - 10 times and add Tict4200- again.
The reaction was allowed to proceed at 0C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then n-hepta/20
Washing with 0- was repeatedly performed, and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was used. At this time, the solid and liquid in the catalyst component were separated and the titanium content in the solid was measured and found to be 383% by weight.

[Overlapping]

During polymerization, 137,111 g of p-)ethyl ruylate was added.
An experiment was conducted in the same manner as in Example 1, except that TI atoms were used as catalyst components. The results obtained are the first
As shown in the table.

Claims (1)

[Scope of Claims] (a) Magnesium fatty acid, mono- and diester of aromatic dicarboxylic acid, (C) halogenated hydrocarbon, and (d) general formula TiX* (wherein X is), halogen element It is. ) A tentacle component for polymerizing olefins obtained by contacting with a titanium halide represented by: (2) Component (a) is suspended in component (e), and the resulting suspension is added to component (d) for contact reaction, at which time,
The catalyst component for polymerizing olefins according to claim (1), which is obtained by coexisting component (b) at any point in time. (3) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the fatty acid magnesium is magnesium stearate, magnesium octoate, magnesium decanoate, or magnesium laurate. (4) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the aromatic dicarboxylic acid mono- and diesters are phthalic acid or terephthalic acid mono- and diesters. (5) The mono- and diester of phthalic acid or terephthalic acid is dimethyl phthalate, dimethyl terephthalate, dibutyl phthalate, diethyl tere7talenite,
The olefin according to claim 4, which is dibutyl phthalate, dibutyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, or ethylpropyl phthalate. Catalyst component for polymerization. (6) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the halogenated hydrocarbon is a chloride of an aromatic or aliphatic hydrocarbon that is liquid at room temperature. . (7) The nuclear halogenated hydrocarbon is chlorobenzene, benzyl chloride, propyl chloride, butylchloride, dichloroethane, trichloroethane, carbon tetrachloride, chloroform, or methylene chloride (claim 0 or ( Catalyst component for polymerizing olefins according to item 2). (8) The halogenated hydrocarbon is propyl chloride,
Claims (1) or (2) which are dichloroethane, chloroform, carbon tetrachloride and methylene chloride
) Catalyst component for polymerizing olefins as described in item 1. (9) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the titanium halide is Tlct4. 00 The olefins are ethylene, propylene and 1
-butene, and is used in the homopolymerization or copolymerization of these catalyst components for olefin polymerization according to claim (1).