JPH07668B2 - Method for producing columnar polyolefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a polyolefin having a special shape, and particularly to a method for producing a columnar polyolefin.

[Conventional technology]

Conventionally, in polyolefins such as polyethylene and polypropylene, many varieties having various characteristics have been developed.

However, in recent years, there has been an increasing demand for polyolefin having superior new properties.

Further, in the conventional technique, in order to impart a special property or form to polyolefin, it is necessary to add a special substance to the polymer obtained by once polymerizing, and to mold it using a special molding machine. It was. However, these methods have required extra steps and have been the cause of product cost ups.

[Problems to be Solved by the Invention] The present inventors arrived at the present invention as a result of conducting research for the purpose of obtaining a polyolefin having new properties from such a viewpoint by a simpler method, that is, only a polymerization operation. ,
This is what we propose here.

[Means for solving problems]

That is, a feature of the present invention is that (a) a magnesium compound obtained by reacting metallic magnesium with a halogenated hydrocarbon is (b) a general formula R ¹ OR ² (wherein R ¹ and R ² are alkyl groups). Group or an aryl group, which may be the same or different, and is treated with an organic compound represented by the following formula (may be simply referred to as an ether hereinafter), and then (c) an aromatic dicarboxylic acid. A catalyst containing a catalyst component obtained by contacting a diester of an acid and (d) a titanium halide represented by the general formula TiX ₄ (where X is a halogen element) (hereinafter simply referred to as “titanium halide”). Another object of the present invention is to provide a method for producing a columnar polyolefin which is characterized by polymerizing olefin in the presence of Polymerization here means homopolymerization and copolymerization.

The magnesium compound used in the present invention needs to be a compound obtained by reacting metallic magnesium with a halogenated hydrocarbon. If necessary, the preparation of the magnesium compound in the present invention is carried out by reacting metallic magnesium and a halogenated hydrocarbon in the presence of iodine or an iodine compound at a temperature substantially from 0 ° C. to the boiling point of the halogenated hydrocarbon used. Is preferably carried out until completion.

As the organic compound represented by the general formula R ¹ OR ² used in the present invention, various ethers are preferable, and aliphatic ethers are particularly 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,
Examples thereof include 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 aliphatic hydrocarbon which is liquid at room temperature.

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.

When obtaining the catalyst component of the present invention, the use ratio of each raw material constituting the catalyst component is optional, and is not particularly limited, as long as it does not adversely affect the performance of the produced catalyst component. Usually, the ethers are used in an amount of 1 ml or more per 1 g of the magnesium compound. The diester of aromatic dicarboxylic acid is 1 g of the magnesium compound
0.01 to 1g, preferably used in the range of 0.05 to 1g, the titanium halide is the magnesium compound
It is used in an amount of 0.1 g or more, preferably 1.0 g or more with respect to 1 g.

Incidentally, in obtaining the catalyst component used in the present invention, after treating the magnesium compound with the ethers, excess ethers are dried under reduced pressure, removed by a method such as excess, and then the aromatic dicarboxylic acid It is preferred to contact the diester and titanium halide. At this time, the treatment of the magnesium compound with the ethers is preferably carried out at a temperature usually from 0 ° C. to the boiling point of the ethers used, and a diester of an aromatic dicarboxylic acid and a titanium halide which are subsequently carried out. The contact is usually carried out at a temperature from 0 ° C. to the boiling point of the titanium halide used for 5 minutes or longer, preferably 10 minutes or longer.

After the contact, the titanium halide is again contacted with the obtained composition. At this time, it is also one of preferred embodiments to wash with an organic solvent such as n-heptane before and after the contact.

It is preferable that these series of operations in the present invention are performed in the absence of oxygen and water.

The catalyst component produced as described above is combined with an organoaluminum compound to form a catalyst for producing a columnar polyolefin. The organoaluminum compound used is used in a molar ratio of 1 to 1000 per mole of titanium atom in the catalyst component. Further, addition and use of a third component such as an electron-donating substance during polymerization are not hindered.

In particular, when an organosilicon compound containing an oxygen atom is added, a columnar polyolefin having extremely high stereoregularity can be obtained while maintaining extremely high activity. Also,
Since the catalyst component in the present invention has an extremely low chlorine content in the component, it does not require a deashing step or the like, and thus can be put to practical use without reducing the characteristics of the columnar polyolefin.

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.

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

〔The invention's effect〕

According to the present invention, an extremely high polymerization activity and stereoregularity can be obtained without any additional treatment such as addition of a special substance to a polymer obtained by polymerization and molding of the polymer by a special molding machine. While maintaining the above, columnar polyolefin can be obtained by only one-step polymerization operation. Since the columnar polyolefin obtained according to the present invention has a very low chlorine content in the catalyst component in the present invention, it is expected to have a wide range of uses such as various composite materials without requiring an operation such as deashing.

〔Example〕

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

Example 1 [Preparation of Magnesium Compound] The capacity was 2.0 l, which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
30 g of magnesium powder, 1.0 g of iodine and 1.2 l of n-butyl chloride were placed in the round-bottomed flask described in (1) and reacted at the boiling point of n-butyl chloride for 5 hours. After the completion of the reaction, the supernatant was removed, the mixture was washed with 500 ml of n-butyl chloride three times, and then dried under reduced pressure to obtain a powdery magnesium compound.

[Preparation of catalyst component]

Fully replaced by nitrogen gas, equipped with a stirrer, capacity 500m
10 g of the magnesium compound obtained as described above and 100 ml of diethyl ether were placed in a round-bottomed flask having a volume of 1 and reacted at the boiling point of diethyl ether for 2 hours. After the reaction,
The solid composition was obtained by removing the supernatant and drying under reduced pressure.

Fully replaced by nitrogen gas, equipped with a stirrer, capacity 500m
5 g of the solid composition and 200 ml of TiCl ₄ were placed in a round-bottomed 1-liter flask, the temperature was raised to 90 ° C., 1.0 ml of dibutyl phthalate was added, and the temperature was further raised to react at 120 ° C. for 2 hours. After the reaction was completed, the supernatant was removed, 200 ml of TiCl ₄ was newly added, and the temperature was 120 ° C.
And reacted for 2 hours.

After completion of the reaction, the mixture was cooled to 40 ° C and washed 10 times with 200 ml of n-heptane to obtain a catalyst component. At this time, when the solid-liquid of the catalyst component was separated and the titanium content of the solid was measured, 2.
It was 36% by weight.

〔polymerization〕

In an autoclave with a stirrer having an internal volume of 2.0 l which was completely replaced with nitrogen gas, 700 ml of n-heptane was charged, and 301 mg of triethylaluminum, 64 mg of phenyltriethoxysilane and then the catalyst components were added while maintaining a nitrogen gas atmosphere. 0.3 mg of titanium atom was charged. After that, 120 ml of hydrogen gas was charged and the temperature was raised to 70 ° C while introducing propylene gas at 6 kg /
Polymerization was carried out for 4 hours while maintaining the pressure of 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 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 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. It should be noted that due to the above polymerization, the length is 2-3 m.
A colorless and transparent columnar polymer having a size of about m was obtained.

Example 2 An experiment was conducted in the same manner as in Example 1 except that dipropyl phthalate was used instead of dibutyl phthalate. The titanium content in the solid content at this time was 2.51% 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. In addition,
A colorless and transparent columnar polymer having a length of about 2 to 3 mm was obtained by the above polymerization.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A magnesium compound obtained by reacting (a) metallic magnesium with a halogenated hydrocarbon,
(B) After being treated with an organic compound represented by the general formula R ¹ OR ² (wherein R ¹ and R ² are alkyl groups or aryl groups, and may be the same or different),
A composition obtained by contacting (c) a diester of an aromatic dicarboxylic acid and (d) a titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element),
Further, (d) a method for producing a columnar polyolefin, which comprises polymerizing olefin in the presence of a catalyst containing a catalyst component obtained by contacting the halide.