JP2823922B2 - Olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for polymerizing olefins, and more particularly, to a method for polymerizing olefins which exhibits excellent polymerization activity and can produce a copolymer having a narrow composition distribution.

Technical Background of the Invention In producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms,
The use of an olefin polymerization catalyst soluble in a hydrocarbon solvent for polymerization has been proposed, for example, in Japanese Patent Publication No. Sho 50-39117, Japanese Patent Laid-Open Publication No. Sho 55-78004.

JP-A-55-78004 mentioned above discloses (A) a hydrocarbon-soluble component formed from an electron donor selected from alcohols, organic acids, aldehydes and amines, and magnesium halide. (B) a liquid transition metal. There is disclosed a (co) polymerization method of olefins, which comprises (co) polymerizing olefins in the presence of a polymerization catalyst obtained by contacting a compound component and (C) an organoaluminum compound.

This olefin polymerization catalyst exhibits excellent polymerization activity and can produce a copolymer having a narrow composition distribution, but has excellent polymerization activity and can produce an ethylene copolymer having a narrow composition distribution. The appearance of a novel catalyst for olefin polymerization has been desired.

Object of the Invention The present invention has been made in view of the prior art as described above, and shows a method of polymerizing olefins, which exhibits excellent polymerization activity, has a narrow composition distribution, and can produce a film with less stickiness. It is intended to provide.

SUMMARY OF THE INVENTION An olefin polymerization method according to the present invention comprises contacting a liquid magnesium compound comprising a halogen-containing magnesium compound and oleyl alcohol, a liquid titanium compound, and a halogen-containing organoaluminum compound (provided that the liquid magnesium compound and the liquid An olefin polymerization catalyst formed by contacting with a titanium compound in advance, except that the liquid titanium compound used in the preparation of the olefin polymerization catalyst has the formula Ti (OR) _g X _{4- g} (wherein R is a hydrocarbon group, X is halogen, and g is 0-4). ] In the presence of the olefin is polymerized or copolymerized.

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization method according to the present invention will be specifically described below.

FIG. 1 shows an example of the preparation process of the olefin polymerization catalyst according to the present invention.

The method for polymerizing an olefin according to the present invention comprises the steps of: contacting a liquid magnesium compound comprising a halogen-containing magnesium compound and oleyl alcohol; a liquid titanium compound; and a halogen-containing organic aluminum compound in the presence of an olefin polymerization catalyst. Olefins are polymerized or copolymerized.

As the halogen-containing magnesium compound, magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride are used, and among them, magnesium chloride is particularly preferably used.

A liquid magnesium compound is prepared by contacting such a halogen-containing magnesium compound with oleyl alcohol. This liquid magnesium compound
The halogen-containing magnesium compound may be in a solution state in which it is dissolved in oleyl alcohol, or the halogen-containing magnesium compound may be in a suspended state in which it is suspended in oleyl alcohol, but is preferably in a solution state.

The contact between the halogen-containing magnesium compound and oleyl alcohol is usually desirably performed at a temperature of 50 ° C. or higher.

In preparing a liquid magnesium compound comprising a halogen-containing magnesium compound and oleyl alcohol, a hydrocarbon solvent may be used.

That is, a liquid magnesium compound may be prepared by substantially dissolving halogen-containing magnesium and oleyl alcohol in a hydrocarbon solvent.

Such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, kerosene; cyclopentane,
Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and cymene; dichloroethane, dichloropropane, trichloroethylene; Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene are used.

When contacting the halogen-containing magnesium compound with oleyl alcohol, oleyl alcohol / MgCl ₂
Is preferably 1 or more, more preferably 1 to 4 in molar ratio.

Next, a liquid titanium compound will be described. As such a titanium compound, Ti (OR) _g X _4-g (where R is a hydrocarbon group, X is halogen, and g is 0 to 4) Is used).

As such a liquid titanium compound, specifically,
Titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O-iC ₃ H ₇ ) Cl ₃ , Ti (On-C _{4 H 9) Cl 3, Ti} (OC 2 H 5) Br 3, Ti (O-iC 3 H 7) Br 3, Ti (OisoC 4 H 9) trihalide, alkoxy titanium such as Br _3; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O-iC ₃ H ₇ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ dihalogenated alkoxy titanium such as _{br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (Oi-C 3 H 7) 3 Cl, Ti (On-C 4 H 9) 3 Cl _{, Ti (OC 2 H 5)} 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H 5) 4, Ti (O-nC 3 H 7) 4, Ti (O- iC ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (OC ₆ H ₁₃ ) ₄ , Ti (OC ₆ H ₁₁ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ , Ti [OCH ₂ ( C ₂ H ₅ ) CHC ₄ H ₉ ] ₄ , Ti (OC _{9 H 19) 4, Ti [OC} 6 H 3 (CH 3) 2] 4, Ti (OC 18 H 35) 4, Ti (OCH 3) 2 (OC 4 H 9) 2, Ti (OC 3 H 7) 3 (OC ₄ H ₉ ), Ti (OC ₂ H ₅ ) ₂ (OC ₄ H ₉ ) ₂ , Ti (OC ₂ H ₅ ) ₂ (OC ₃ H ₇ ) ₂ , Ti (OC ₂ H ₅ ) (OC ₁₈ H _{35) 3, Ti (OC 2} H 5) 2 (OC 18 H 35) 2, Ti (OC 2 H 5) 3 (OC 18 H 35) and the like can be exemplified tetraalkoxytitanium such. Among these, 1 ≦
Compounds satisfying g ≦ 4 are preferable, compounds satisfying 2 ≦ g ≦ 4 are more preferable, and tetraalkoxytitanium is particularly preferably used.

Next, the halogen-containing organoaluminum compound will be described. Examples of the halogen-containing organoaluminum include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide Alkyl aluminum sesquihalides such as; aluminum aluminum dichloride, propyl aluminum dichloride, alkyl aluminum dihalides such as butyl aluminum dibromide; partially halogenated alkyl aluminum; ethyl aluminum ethoxycyclolide, butyl aluminum butoxycyclolide, ethyl aluminum Parts such as ethoxy bromide Such alkoxylated and halogenated alkyl aluminum is used.

In the present invention, the liquid magnesium compound, the liquid titanium compound, and the halogen-containing organoaluminum compound as described above are supplied to and contacted with a polymerization reaction vessel, and the olefin is polymerized in the presence of the obtained olefin polymerization catalyst. Polymerize or copolymerize.

At that time, each component can be independently supplied to the polymerization reactor, or the liquid magnesium compound component and the halogen-containing organoaluminum compound component are partially or entirely brought into contact with each other before being supplied to the polymerization reactor. Alternatively, the liquid titanium compound component and the halogen-containing organoaluminum compound may be partially or entirely brought into contact with each other before being supplied to the polymerization reactor. However,
An embodiment in which the liquid magnesium compound component and the liquid titanium compound component unit are brought into contact with each other before being supplied to the polymerization reactor is excluded from the present invention.

In carrying out the polymerization reaction of the olefin, the liquid titanium compound is used in an amount such that the titanium atom is 0.0005 to about 1 mmol, preferably about 0.001 to about 0.5 mmol per reaction volume 1, and the halogen-containing organoaluminum compound is Aluminum / titanium (atomic ratio) is about 1 to about 2000,
It is desirable to use an amount that will preferably be from about 5 to about 100.

The molar ratio of the titanium compound / MgCl ₂ is preferably 0.04 to 0.30, and more preferably 0.05 to 0.20.

The olefin polymerization using the olefin polymerization catalyst as described above can be performed in the form of copolymerization of olefins or copolymerization of olefin and polyene. Examples of the olefin that can be used for the polymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene. And the like.
The polyene includes butadiene, isoprene,
Examples thereof include 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene.

The catalyst for olefin polymerization as described above is particularly useful for copolymerization of ethylene.
In particular, it is preferable to carry out the copolymerization so that ethylene is contained at about 75% by weight or more. Then, using this olefin polymerization catalyst, ethylene and a small amount of α-olefin are copolymerized, and the density is 0.870 to 0.960 g to m ³ , preferably 0.880 to
A low-density ethylene copolymer having a narrow composition distribution of 0.950 g to m ³ can be obtained.

In the method of the present invention, olefin polymerization is carried out in a hydrocarbon solvent using the catalyst component. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof; alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane and halogen derivatives thereof; Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene, and halogen derivatives such as chlorobenzene. Further, the olefin itself used for the polymerization can be used as a solvent.

The polymerization temperature of the olefin is desirably from about 20 to about 300C, preferably from about 65 to about 250C. The polymerization pressure is atmospheric pressure to 3000 kg / cm ² -G, preferably 2 to about 100 kg / G.
It is preferably cm ² -G, especially about 2 to about 50 kg / cm ² -G.

In olefin polymerization, it is preferable to make hydrogen coexist in order to control the molecular weight.

The polymerization can be carried out batchwise or continuously. Further, it can be performed in two or more stages under different conditions.

Effect of the Invention In the present invention, in the presence of a catalyst for olefin polymerization formed by contacting a liquid magnesium compound prepared using oleyl alcohol, a liquid titanium compound, and a halogen-containing organoaluminum compound, especially ethylene and Since the copolymer is copolymerized with an α-olefin, an ethylene / α-olefin copolymer having a narrow composition distribution and thus having a small amount of n-decane-soluble components and a low stickiness when formed into a film can be obtained. The olefin polymerization catalyst obtained using alcohols other than oleyl alcohol, for example, 2-ethylhexanol, compared to the olefin polymerization catalyst obtained using oleyl alcohol,
The polymerization activity is inferior, and the composition distribution of the obtained ethylene / α-olefin copolymer becomes wide.

The “amount of n-decane-soluble component” here is specifically measured by the following method. That is, in this specification, a dissolution reaction is carried out at 140 to 145 ° C. while stirring a solution of n-decane (500 ml) to which polymer particles (3 g) are added, and then stirring is stopped. After cooling to 23 ° C. and further keeping at 23 ° C. for 5 hours, the mixture was separated by filtration using a G-4 glass filter, and the weight fraction of the polymer obtained by removing n-decane from the obtained filtrate was calculated. Calculate and set this as “23 ° C. n-decane soluble component amount”.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 [Preparation of liquid magnesium compound] 47.6 g of commercially available anhydrous magnesium chloride was suspended in n-decane 1 under a nitrogen atmosphere, and 403 g of oleyl alcohol was suspended.
(3 times mol with respect to magnesium chloride) was added. The temperature was gradually raised with stirring and reacted at 145 ° C. for 5 hours, and then cooled to room temperature to obtain a liquid magnesium compound.

[Polymerization] After sufficiently purging the autoclave having an internal volume of 2 with nitrogen, 750 ml of cyclohexane and 4-methyl-1-pentene 2 were added.
After charging 50 ml, the temperature was raised to 165 ° C, 11.6 mmol of hydrogen,
0.52 mmol of ethylaluminum sesquichloride, the liquid magnesium compound having a concentration of 0.
11 mmol and then 0.01 mmol of Ti (OC ₂ H ₅ ) ₄ were simultaneously injected with ethylene gas, and the polymerization was started at a total pressure of 25 kg / cm ² gauge.

After that, only ethylene gas was supplied, and the total pressure was 25 kg / cm ²
While maintaining the gauge, polymerization was performed at 170 ° C. for 40 minutes. 40 minutes later,
The polymerization was stopped by ethanol injection.

The produced polymer was dried under reduced pressure at 80 ° C. overnight. The yield of the obtained copolymer was 84.4 g, and the polymerization activity was 8440 g copolymer / mmol-Ti. The density of the copolymer is 0.905 g / c
The content of m ³ , MI 2.0 and n-decane soluble components was 4.5% by weight.

Example 2 [Preparation of liquid magnesium compound] 47.6 g of commercially available anhydrous magnesium chloride was suspended in n-decane 1 under a nitrogen atmosphere, and 336 g of oleyl alcohol was suspended.
(2.5 times mol with respect to magnesium chloride) was added.
The temperature was gradually raised while stirring, and after reacting at 145 ° C. for 8 hours, the temperature was lowered to room temperature to obtain a liquid magnesium compound.

[Polymerization] The polymerization was performed in the same manner as in Example 1 except that the amount of ethyl aluminum sesquichloride was changed to 0.38 mmol and the amount of the liquid magnesium compound was changed to 0.083 mmol in terms of magnesium atom in the polymerization of Example 1.

 Table 1 shows the results.

Example 3 [Preparation of liquid magnesium compound] In Example 2, the addition amount of oleyl alcohol was changed to 26.
It was prepared in the same manner as in Example 2 except that the amount was 9 g (2 times the mol of magnesium chloride).

[Polymerization] In the polymerization of Example 1, 0.35 mmol of ethyl aluminum sesquichloride, 0.0148 mmol of the magnesium compound in terms of magnesium atom, Ti (OC ₂ H ₅ )
Example ₄ was carried out in the same manner as in Example 1 except that ₄ was changed to 0.0117 mmol.

 Table 1 shows the results.

Example 4 In Example 1, Ti (O ₂ H ₅ ) ₄ was replaced with Ti (O 2
The same procedure as in Example 1 was carried out except that CH ₂ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ CH ₃ ) ₄ was used.

Example 5 In Example 1, Ti (O ₂ H ₅ ) ₄ was replaced with Ti (O 2
The procedure was performed in the same manner as in Example 1 except that nC ₄ H ₉ ) ₄ was used.

Comparative Example 1 [Preparation of Liquid Magnesium Compound] 47.6 g of commercially available anhydrous magnesium chloride was suspended in n-decane 1 under a nitrogen atmosphere, and 195 g of 2-ethylhexanol (3 times the molar amount of the base magnesium) was added thereto. did. The temperature was gradually raised while stirring, and the mixture was reacted at 145 ° C. for 5 hours, and then cooled to room temperature to obtain a liquid magnesium compound.

[Polymerization] The polymerization was carried out in exactly the same manner as in Example 1 using the magnesium compound.

 Table 1 shows the results.

Comparative Example 2 [Preparation of liquid magnesium compound] A liquid magnesium compound was prepared in the same manner as in Comparative Example 1, except that 153 g of 2-ethylhexanol was used (2.35 times the molar amount of magnesium chloride).

[Polymerization] The same procedure as in Example 2 was carried out using the magnesium compound.

 Table 1 shows the results.

Comparative Example 3 [Preparation of Liquid Magnesium Compound] In Comparative Example 1, 237 g of 1-decanol was used instead of 2-ethylhexanol (4 to magnesium chloride).
Except for the use of the compound of Example 1, except that the compound was prepared in the same manner as in Comparative Example 1.

[Polymerization] The polymerization was carried out in exactly the same manner as in Example 1 using the magnesium compound.

 Table 1 shows the results.

Comparative Example 4 [Preparation of Liquid Magnesium Compound] Except that, in Comparative Example 1, 204 g of 1-hexanol (4 times mol with respect to magnesium chloride) was used instead of 2-ethylhexanol and reacted at 80 ° C. for 10 hours. And prepared in the same manner as in Comparative Example 1.

[Polymerization] The polymerization was carried out in exactly the same manner as in Example 1 except that the addition amount of ethyl aluminum sesquichloride was 0.80 mmol using the magnesium compound.

 Table 1 shows the results.

[Brief description of the drawings]

FIG. 1 is an explanatory view of the olefin polymerization method according to the present invention.

Claims (1)

(57) [Claims] 1. A liquid magnesium compound comprising a halogen-containing magnesium compound and oleyl alcohol, a liquid titanium compound, and a halogen-containing organoaluminum compound are contacted (provided that the liquid magnesium compound and the liquid titanium compound are brought into contact in advance. [The liquid titanium compound used for the preparation of the olefin polymerization catalyst is represented by the formula Ti (OR) _g X _4-g (where R is a hydrocarbon) X is a halogen, and g is 0 to 4). ] The olefin is polymerized or copolymerized in the presence of the olefin.