JP2868568B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefin, and more particularly, to an olefin having excellent polymerization activity and capable of producing a copolymer having a narrow composition distribution. The present invention relates to a polymerization catalyst and a method for polymerizing an olefin.

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 polymerization hydrocarbon solvent is disclosed in, for example, Japanese Patent Publication No. 50-39117,
It is proposed in, for example, JP-A-55-78004.

JP-A-55-78004 mentioned above discloses that (A) a hydrocarbon-soluble component formed from an electron donor selected from an alcohol, an organic acid, an aldehyde and an amine, and a 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 has excellent polymerization activity and a narrow composition distribution, and is capable of producing a film with low stickiness and an olefin polymerization catalyst. It is intended to provide a method for polymerizing an olefin.

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises: [A] a liquid titanium catalyst component comprising a halogen-containing magnesium compound, oleyl alcohol and a titanium compound, and [B] a halogen-containing organoaluminum compound. I have.

The titanium catalyst component in a liquid state as described above can be prepared by contacting a mixture of halogen-containing magnesium and oleyl alcohol with a titanium compound at a temperature of 40 ° C. or higher.

The liquid titanium catalyst component as described above can be prepared by contacting a halogen-containing magnesium compound, oleyl alcohol, and a titanium compound at a temperature of 40 ° C. or higher.

Further, the olefin polymerization method according to the present invention is characterized in that an olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst as described above.

DETAILED DESCRIPTION OF THE INVENTION The catalyst for olefin polymerization 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 olefin polymerization catalyst according to the present invention comprises: [A] a liquid titanium catalyst component comprising a halogen-containing magnesium compound, oleyl alcohol, and a titanium compound [provided that the titanium catalyst component [A] is used. The titanium compound is a tetravalent titanium compound represented by the formula Ti (OR) _g X _4-g (where R is a hydrocarbon group, X is a halogen, and g is 0 to 4). And [B] a halogen-containing organoaluminum compound.

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

As the titanium compound, a tetravalent titanium compound represented by Ti (OR) _g X _4-g (where R is a hydrocarbon group, X is a halogen, and g is 0 to 4) is used. .

As such a titanium compound, specifically, TiCl
₄ , titanium tetrahalides such as 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 Trihalogenated alkoxy titanium such as H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iC ₃ H ₇ ) Br ₃ , Ti (O isoC ₄ H ₉ ) 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; T
i (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 (OiC 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) illustrate and tetraalkoxytitanium such as be able to. Among these, 1 ≦ g ≦
4, and more preferably 2 ≦ g ≦ 4, particularly preferably tetraalkoxytitanium.

The titanium catalyst component [A] in the liquid state according to the present invention is a substantially homogeneous solution comprising the halogen-containing magnesium, oleyl alcohol, and the titanium compound as described above.

As the titanium catalyst component [A] in a liquid state, it is preferable to prepare a mixture of, for example, halogen-containing magnesium and oleyl alcohol, and then contact the mixture with a titanium compound. The mixture comprising the halogen-containing magnesium and oleyl alcohol may be in a solution state or a suspension state, but is preferably in a solution state. Further, a preferable method is to change the solution state while mixing the halogen-containing magnesium compound, oleyl alcohol and titanium compound.

At this time, at 40 ° C. or higher, preferably 40 to 200 ° C., more preferably 50 to 150 ° C., a mixture of halogen-containing magnesium and oleyl alcohol, and a titanium compound for 1 minute or more, preferably 15 minutes to 24 hours, Particularly preferably 30
It is desirable that the reaction be carried out by contacting for minutes to 15 hours.

[A] The titanium catalyst component in a liquid state is obtained by simultaneously mixing halogen-containing magnesium, oleyl alcohol and a titanium compound at 40 ° C. or higher, preferably 40 to 200 ° C., more preferably 50 to 150 ° C., for 1 minute or longer, preferably 15 to 150 ° C. It can also be prepared by contacting and reacting for minutes to 24 hours, particularly preferably for 30 minutes to 15 hours.

In preparing the titanium catalyst component in a liquid state comprising a halogen-containing magnesium, a titanium compound and oleyl alcohol, a hydrocarbon solvent may be used.

That is, the halogen-containing magnesium and oleyl alcohol may be substantially dissolved in the hydrocarbon solvent and then contacted with the titanium compound, or the halogen-containing magnesium compound, the oleyl alcohol and the titanium compound may be substantially dissolved in the hydrocarbon solvent. You may contact.

Such hydrocarbon solvents include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as 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.

The halogen-containing magnesium, titanium compound and oleyl alcohol are preferably used in the following amounts.

Oleyl alcohol / MgCl ₂ is usually 1 or more, preferably 1 to 4 in molar ratio.

Titanium compound / MgCl _2, the 0.04 to 0.30 preferably in a molar ratio of 0.05 to 0.20.

[B] The halogen-containing organoaluminum used in the present invention includes dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkylaluminums such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Sesquihalides; alkyl aluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like; partially aluminum halides; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide and the like Partially alkoxylated and halogenated It can be exemplified Le kill aluminum.

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 olefin polymerization catalyst according to the present invention as described above is particularly useful for copolymerization of ethylene. In the copolymerization of ethylene, it is particularly preferable to carry out the copolymerization so that ethylene is contained at about 75% by weight or more. preferable. The olefin polymerization catalyst according to the present invention comprises ethylene and a small amount of α-
It is copolymerized olefins, density 0.87~0.96g / m ^3,
In particular, a low-density ethylene copolymer having a narrow composition distribution of 0.88 to 0.95 g / m ³ can be obtained.

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

In carrying out the polymerization reaction, titanium atoms are contained in an amount of 0.0005 to about 1 mmol, more preferably about 0.005 mol per reaction volume.
1 to about 0.5 mmol, and the organoaluminum compound may be used in an aluminum / titanium (atomic ratio) of about 1 to about 2000, preferably about 5 to about 100. The polymerization temperature of the olefin is about 20 to about 300 ° C, preferably about 65 ° C.
Preferably, it is from about 250 ° C. The polymerization pressure is atmospheric pressure of about 3000 kg / cm ² -G, preferably 2 to about 100 kg / cm ² -G,
In particular, it is preferably about 5 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, since ethylene and α-olefin are copolymerized in the presence of an olefin polymerization catalyst prepared using oleyl alcohol, the composition distribution is narrow, and therefore the amount of n-decane soluble component When the film is low in amount, an ethylene / α-olefin copolymer having low stickiness can be obtained. The olefin polymerization catalyst obtained by using alcohols other than oleyl alcohol, for example, 2-ethylhexanol, is inferior in polymerization activity to the olefin polymerization catalyst obtained by using oleyl alcohol, and the obtained ethylene -The composition distribution of the α-olefin copolymer also widens.

The “amount of n-decane-soluble component” here is specifically measured by the following method. That is, in the present 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. Cool to 23 ° C and further
After keeping at 23 ° C. for 5 hours, the polymer 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. 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 titanium catalyst component (A) 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 obtained.
(3 times mol with respect to magnesium chloride) was added thereto, and the temperature was gradually increased while stirring, followed by reaction at 135 ° C. for 3 hours. The solid completely disappeared, and a colorless transparent liquid was obtained.

After the temperature of this solution was lowered to 110 ° C., it was added to Ti (OC ₂ H ₅ ) ₄
Was added and the reaction was continued at 110 ° C. for 5 hours. The mixture of magnesium chloride / oleyl alcohol / Ti (OC ₂ H ₅ ) ₄ thus obtained did not precipitate solids even when cooled to room temperature, and remained a clear homogeneous solution. At this time, the molar ratio of titanium / magnesium is 0.09.

[Polymerization] An autoclave having an internal volume of 2 liters was sufficiently purged with nitrogen, and then 100 ml of 4-methyl-1-pentene and 9 ml of cyclohexane.
Then, the temperature was raised to 170 ° C. When the temperature reached 170 ° C., 150 ml of hydrogen and ethylene were injected until the gauge pressure reached 16 kg / cm ² . Next, 0.47 mmol of ethylaluminum sesquichloride was added to the system using an addition pot attached to the autoclave, and subsequently the Ti catalyst obtained above was added in an amount of 0.07 mmol in terms of Ti atoms. Polymerization was carried out at 170 ° C. for 40 minutes while continuously supplying ethylene so that the total pressure was maintained at 16 kg / cm ² G.

After completion of the polymerization, the temperature was lowered and the pressure was released to obtain a copolymer. The yield of the obtained copolymer was 75.0 g, and the polymerization activity was 7,500 g copolymer / mmol-Ti. The density of the copolymer is 0.907 g / c
The amount of soluble components in m ³ , MI 2.5 and n-decane was 2.5% by weight.

Comparative Example 1 [Preparation of titanium catalyst component] 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 was obtained.
(3 times mol with respect to magnesium chloride), the temperature was gradually increased while stirring, and the reaction was carried out at 130 ° C. for 1 hour. The solid completely disappeared, and a colorless transparent liquid was obtained.

After the temperature of the solution was lowered to 110 ° C., ₄ parts of Ti (OC ₂ H ₅ ) ₄ were added thereto.
5 mmol was added and the reaction was continued at 110 ° C. × 5 hours. Thus, magnesium chloride / 2-ethylhexanol / Ti
(OC ₂ H ₅ ) _{4 A} homogeneous transparent solution was obtained.

At this time, the molar ratio of titanium / magnesium is 0.09.

[Polymerization] Polymerization in Example 1, without using magnesium chloride / oleyl alcohol _{/ Ti (OC 2 H 5)} 4 mixture, wherein the magnesium chloride / 2-ethylhexanol _{/ Ti (OC 2 H 5)} 4 mixed Polymerization was carried out in the same manner as in Example 1 except that the liquid was used.

The yield of the obtained copolymer was 42.0 g, and the polymerization activity was 4
It was 200 g copolymer / mmol-Ti.

The density of the copolymer was 0.907 g / cm ³ , MI 2.7, and the amount of n-decane soluble components was 7.0% by weight.

Comparative Example 2 In Example 1, 1-
A homogeneous transparent solution of magnesium chloride / 1-hexanol / Ti (OC ₂ H ₅ ) ₄ was obtained in the same manner as in Example 1 by using 204 g of hexanol (4 times the mol of magnesium chloride). At this time, the molar ratio of titanium / magnesium is
0.09.

In the polymerization of Example 1, the magnesium chloride / 1-hexanol / Ti (OC ₂ H ₅ ) ₄ mixture was used without using the magnesium chloride / oleyl alcohol / Ti (OC ₂ H ₅ ) ₄ mixture in the polymerization of Example 1. The polymerization was carried out in the same manner as in Example 1 except that the addition amount of ethyl aluminum sesquichloride was changed to 0.80 mmol.

The yield of the obtained copolymer was 65.1 g, and the polymerization activity was 6
It was 510 g copolymer / mmol-Ti.

The density of the copolymer was 0.909 g / cm ³ , MI was 1.7, and the amount of n-decane soluble components was 6.8% by weight.

Comparative Example 3 The procedure of Example 1 was repeated, except that the temperature at which the magnesium chloride / oleyl alcohol solution was reacted with Ti (OC ₂ H ₅ ) ₄ was changed to 20 ° C.

The yield of the obtained copolymer was 49.5 g, and the polymerization activity was 4
It was 950 g copolymer / mmol-Ti.

The density of the copolymer was 0.907 g / cm ³ , MI was 1.7, and the amount of n-decane soluble components was 4.5% by weight.

Example 2 The amount of oleyl alcohol added in Example 1 was 335.6 g.
(2.5 times mol with respect to magnesium chloride) and Ti
A homogeneous solution was obtained in the same manner as in Example 1 except that the amount of (OC ₂ H ₅ ) ₄ added was 60 mmol. At this time, the molar ratio of titanium / magnesium was 0.12.

The polymerization was conducted in the same manner as in Example 1 except that the amount of ethylaluminum sesquichloride was changed to 0.34 mmol.
Polymerization was carried out in the same manner as described above.

The yield of the obtained copolymer was 80.2 g, and the polymerization activity was 8
It was 020 g copolymer / mmol-Ti.

The density of the copolymer was 0.905 g / cm ³ , MI 1.5, and the amount of n-decane soluble components was 2.8% by weight.

Example 3 The polymerization in Example 1 was repeated except that 250 ml of 4-methyl-1-pentene, 750 ml of cyclohexane, and 250 m2 of hydrogen were used.
l, The procedure was the same as in Example 1, except that ethylene was continuously supplied at a gauge pressure of 25 kg / cm ² .

The yield of the obtained copolymer was 125.0 g and the polymerization activity was 12
It was 500 g copolymer / mmol-Ti. The density of the copolymer was 0.902 g / cm ² G, MI 2.4, and the amount of n-decane soluble components was 6.0% by weight.

Examples 4 to 8 Polymerization was carried out in the same manner as in Example 3, except that the molar ratio between titanium and magnesium and the type of the titanium compound were changed.

 Table 1 shows the results.

Example 9 [Preparation of titanium catalyst component (A)] Under an atmosphere of nitrogen, 47.6 g of commercially available anhydrous magnesium chloride was suspended in n-decane 1, and 336 g of oleyl alcohol (2.5 moles relative to magnesium chloride) was added thereto. And 60 mmol of Ti (OC ₂ H ₅ ) ₄ were added, the temperature was gradually raised while stirring, and the reaction was carried out at 120 ° C. for 8 hours. At this time, the molar ratio of titanium / magnesium is 0.12.

[Polymerization] In the polymerization, the amount of ethyl aluminum sesquichloride added in Example 3 was 0.35 mmol and the amount of Ti
Polymerization was carried out in the same manner as in Example 3, except that the amount of the catalyst added was 0.0113 mmol in terms of Ti atoms.

The yield of the obtained copolymer was 145.6 g, and the polymerization activity was
It was 12880 g copolymer / mmol-Ti. The density of the copolymer was 0.907 g / cm ³ , MI 2.7, and n-decane soluble component amount 2.8% by weight.

Example 10 [Preparation of titanium catalyst component (A)] Under an atmosphere of nitrogen, 47.6 g of commercially available anhydrous magnesium chloride was suspended in n-decane 1, and 336 g of oleyl alcohol was added thereto (2.5 times the molar amount of magnesium chloride). Was added, and the temperature was gradually raised with stirring, and the reaction was carried out at 120 ° C. for 5 hours. Subsequently, 60 mmol of Ti (OC ₂ H ₅ ) ₄ was added thereto, and the mixture was further reacted at 120 ° C. for 5 hours. At this time, the molar ratio of titanium / magnesium is 0.12.

[Polymerization] The polymerization was carried out in the same manner as in Example 9 except that the amount of the Ti catalyst added was changed to 0.0106 mmol in terms of Ti atoms.

The yield of the obtained copolymer was 127.4 g, and the polymerization activity was
It was 12010 g copolymer / mmol-Ti. The density of the copolymer was 0.906 g / cm ³ , MI 1.9, and n-decane soluble component amount 3.1% by weight.

Example 11 [Preparation of Titanium Catalyst Component (A)] Under a nitrogen atmosphere, 47.6 g of commercially available anhydrous magnesium chloride was suspended in n-decane 1, and 268 g of oleyl alcohol (twice the mol of magnesium chloride) was added thereto. and
After adding 60 mmol of Ti (OC ₂ H ₅ ) ₄ , the temperature was gradually raised while stirring, and the reaction was carried out at 120 ° C. for 10 hours. At this time,
The molar ratio of magnesium is 0.12.

[Polymerization] The polymerization was carried out in the same manner as in Example 9, except that the amount of the Ti catalyst added was 0.0117 mmol in terms of Ti atoms.

The yield of the obtained copolymer was 118.8 g, and the polymerization activity was
It was 10150 g copolymer / mmol-Ti. The density of the copolymer was 0.907 g / cm ³ , MI 2.0, and the amount of n-decane soluble components was 2.9% by weight.

[Brief description of the drawings]

FIG. 1 is a flow chart showing an example of a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (5)

(57) [Claims] [1] A titanium catalyst component in a liquid state comprising [A] a halogen-containing magnesium compound, oleyl alcohol, and a titanium compound [where the titanium compound used for the preparation of the titanium catalyst component [A] has the formula Ti (OR)
_g X _4-g (wherein R is a hydrocarbon group, X is a halogen, and g is 0-4). ] And [B] a halogen-containing organoaluminum compound. 2. The olefin polymerization catalyst according to claim 1, wherein the oleyl alcohol / halogen-containing magnesium compound (molar ratio) is 1 or more. 3. The titanium catalyst component in a liquid state is obtained by contacting a mixture of a halogen-containing magnesium compound and oleyl alcohol with a titanium compound at a temperature of 40 ° C. or higher. The catalyst for olefin polymerization according to Item. 4. The method according to claim 1, wherein the titanium catalyst component in a liquid state is obtained by bringing a halogen-containing magnesium compound, oleyl alcohol, and a titanium compound into contact with each other at a temperature of 40 ° C. or higher. Olefin polymerization catalyst. 5. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.