JPH0745543B2 - Process for producing olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer. More specifically, it relates to a method for producing a high-order-regulating polyolefin by using a catalyst composed of a titanium-based solid component supported on an Mg compound and a titanium dialkyl compound having a bridge-type ligand.

[Conventional technology and its problems]

The titanium-based solid component supported on the Mg compound can be used as a catalyst for olefin polymerization in combination with an organoaluminum compound, but it is known that the polymer produced has low stereoregularity. In such a catalyst system, a method of adding various electron donors at the time of polymerization to improve stereoregularity has been known (John Boor, Jr., “Ziegle.
r−Natta Catalysts and Polymerizations ", Academic P
ress).

With this titanium-based solid catalyst supported on this conventional Mg compound,
In order to obtain a highly stereoregulatory polymer, an electron donor must be added as a third component in addition to the organoaluminum compound, and if the addition amount of the electron donor is increased to increase the stereoregularity. However, there is a problem that the polymerization activity is lowered.

In addition, the titanium-based solid catalyst supported on the Mg compound and (Me _n
A method of polymerizing an olefin with a catalyst containing a —Cp) ₂ TiMe ₂ (n = 0,1) compound has been known (Makromo
l. Chem., Rapid Commun. 7, p. 719 (1986)). It should be noted that there is no description in this paper of using a titanium compound having a bridge-type ligand.

As a result of repeated studies to solve the above problems, the present inventors have found that a catalyst composed of a titanium-based solid component supported on an Mg compound and a titanium dialkyl compound having a bridge-type ligand has two components. It was found that a polymer having a high stereoregularity can be produced even though it is a system, and the present invention has been accomplished.

[Means for Solving the Problems] That is, the present invention provides (A) a titanium-based solid component supported on an Mg compound produced through the following reactions of steps I to III, and I. anhydrous magnesium dihalide, General formula Ti (OR ¹ ) ₄
In ortho titanate represented and / or the general formula ^{R 2 O-Ti (OR 3} ) (OR 4) m consists polytitanic acid ester represented by OR ⁵ (wherein ^{R 1, R 2, R 3} , R ⁴ and R ⁵ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, m is a number of 2 to 20), and a saturated group having 1 to 20 carbon atoms or An unsaturated monohydric or polyhydric alcohol is mixed and dissolved in an inert hydrocarbon solvent to obtain (Component A), and II. (Component A) contains an aliphatic or aromatic carbon atom having 2 to 24 carbon atoms. Mono- or polycarboxylic acid ester (hereinafter referred to as organic acid ester), a general formula AlX _n R ⁸ _3-n (where,
X is Cl or Br, R ⁸ is a cycloalkyl group having a carbon number of 3 to 20, n is a number of 0 to 3), and an aluminum halide represented by the general formula SiX ₁ R ▲ ⁶ _4-l or SiX _p
(OR ⁷ ) _4-p (wherein X is Cl or Br, R ⁶ and R ⁷ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and 1 or p is (Component B) composed of a silicon halide represented by the formula (1 to 4) is mixed and reacted to precipitate a solid (hereinafter referred to as a solid product (I)), and III. , The general formula TiX _q (OR ⁹ ) _4-q (wherein X is Cl or Br, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q Is a number of 1 to 4) and is a titanium halide and / or a vanadyl halide or a halogenated compound represented by the general formula VOX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ) _4-t . A reaction for obtaining a solid (hereinafter referred to as a solid product (II)) by reacting (component C) composed of vanadium.

(B) A titanium dialkyl compound having as a bidentate ligand a bridge-type compound in which two groups selected from an indenyl group and a partial hydride thereof are bonded via a lower alkyl group. The present invention relates to a method for producing an olefin polymer, which comprises polymerizing an olefin.

The method for producing the titanium-based solid component (A) supported on the Mg compound as the catalyst component used in the method of the present invention is a method using MgCl ₂ , a method using Mg (OR) ₂ , and RMgCl. There are a method of using, a method of using RMgR ′, a method of using metal Mg, and the like (where R and R ′ are alkyl groups).

An Mg compound-supported titanium-based solid component produced by any method can be used, but more specifically, Japanese Patent Application No. 59-
The manufacturing method shown in 208775 (Japanese Patent Laid-Open No. 61-85408) can be mentioned.

Another catalyst component, titanium dialkyl compound (B), used in the method of the present invention is a titanium dialkyl compound having a bridge type compound as a bidentate ligand. Examples of the bridge-type ligand include an ethylenebis (indenyl) group, an ethylenebis (4,5,6,7-tetrahydro-1-indenyl) group, a 1,3-propanedinylbis (indenyl) group, and a 1,3 -Propandinylbis (4,5,6,7-tetrahydro-1-inidenyl) group and the like can be mentioned. The above-mentioned titanium dialkyl compound is a known titanium dihalide compound having a bridge type ligand (Journal of Organometallic Chem., 232
Volume, 233 (1982), and 322, 65 (1987),
It is obtained by reacting alkyllithium. Moreover, a methyl group, an ethyl group, etc. can be mentioned as an alkyl group.

Titanium dialkyl compounds that can be used in the method of the present invention include ethylenebis (indenyl) titanium dimethyl, ethylenebis (indenyl) titanium diethyl, ethylenebis (4,5,6,7-tetrahydro-
1-indenyl) titanium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium diethyl, 1,3-propanedinylbis (indenyl)
Titanium dimethyl, 1,3-propanedinylbis (indenyl) titanium diethyl, 1,3-propanedinylbis (4,5,6,7-tetrahydro-1-indenyl) titanium dimethyl, 1,3-propanedinylbis (4 , 5,6,7-Tetrahydro-1-indenyl) titanium diethyl, etc., preferably ethylenebis (indenyl) titanium dimethyl and 1,3-propanedinylbis (indenyl) titanium dimethyl.

In the method of the present invention, the olefin used in the polymerization reaction is an α-olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, It is also possible to use two or more kinds of mixed components for the polymerization. Also, the above α-
It is also possible to sequentially use olefins and subject them to block copolymerization. Furthermore, butadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-
Dienes such as nonadiene, 1,9-decadiene,
Alternatively, it is also effective for copolymerizing a cyclic olefin such as cyclopropane, cyclobutane, cyclohexene, norbornene, and dicyclopentadiene with an α-olefin.

As the polymerization method, either liquid phase polymerization such as suspension polymerization or solution polymerization, or gas phase polymerization can be used. As a polymerization solution for liquid phase polymerization, pentane, hexane, octane, aliphatic hydrocarbons such as decane, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, petroleum fractions such as gasoline, kerosene, and light oil are used. Of these, aromatic hydrocarbons are preferable.

The olefin pressure of the reaction system is normal pressure to 50 kg / cm ² G, and the polymerization temperature is -50 to 230 ° C, preferably -20 to 200 ° C.

In the method of the present invention, both (A) a titanium-based solid component supported on a Mg compound and (B) a titanium dialkyl compound are fed to a polymerization vessel, respectively, and 5 minutes to 3 hours, preferably 5 minutes to 3 hours before feeding an olefin. It is suitable to stir for 30 minutes to 2 hours. Concentration of both components in the polymerization system,
The molar ratio is not particularly limited, but preferably,
The molar ratio of the Ti component of (B) / (A) is in the range of 0.1 to 100.

Isotactic index (II) used in the present invention
For example, in the production of a propylene polymer, the term "stereoregularity" refers to the ratio of the polymerization of isotactic polypropylene as an insoluble matter in n-hexane (20 ° C) to the total amount of polymer production of 100. is there.

[Effects of the Invention] As a titanium dialkyl compound to be combined with a titanium type solid component supported on a Mg compound, a bridge type compound in which two groups selected from indenyl and its partial hydride are bonded via a lower alkyl group is used. According to the method of the present invention using a titanium dialkyl compound having a bidentate ligand, as is clear from the examples and comparative examples described below, the stereoregularity is higher than that of the conventional catalyst system despite the two-component system. A polymer is obtained.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

Example 1 500 ml of purified toluene was placed in a sus autoclave having an internal volume of 1.5 L, which had been sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the above-mentioned method (A) was added to 0.06 mmo as a Ti component.
1, and ethylenebis (indenyl) titanium dimethyl (0.58 mmol) were sequentially added, and the temperature was raised to 30 ° C. Stir at this temperature for 1 hour, then add propylene to this at a total pressure of 1.
It was continuously introduced so as to maintain 0 kg / cm ² G, and polymerization was carried out for 2.0 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polymer was dried. As a result, the polymer
5.2 g were obtained, II was 97.

Example 2 500 ml of purified toluene was added to a sus autoclave with an internal volume of 1.5 L that had been sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the above-mentioned method (A) was used as a Ti component in an amount of 0.05 mmo.
1, and ethylenebis (indenyl) titanium dimethyl (0.51 mmol) were sequentially added, and the temperature was raised to 30 ° C. Stir at this temperature for 1 hour, then add propylene to this at a total pressure of 1.
It was continuously introduced so as to maintain 0 kg / cm ² G, and polymerization was carried out for 4.0 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polymer was dried. As a result, the polymer
7.6 g was obtained, II was 96.

Example 3 500 ml of purified toluene was added to a sus autoclave having an internal volume of 1.5 L which had been sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the method of the above (A) was 0.06 mmo as Ti component.
1, and ethylenebis (indenyl) titanium dimethyl (0.59 mmol) were sequentially added, and the temperature was raised to 50 ° C. Stir at this temperature for 1 hour, then add propylene to this at a total pressure of 7.
It was continuously introduced so as to maintain 0 kg / cm ² G, and polymerization was carried out for 2.0 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polymer was dried. As a result, the polymer
28.8 g was obtained and II was 94.

Example 4 500 ml of purified toluene was added to a sus autoclave having an internal volume of 1.5 L, which had been sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the above-mentioned method (A) was 0.06 mmo as Ti component.
1, and 1,3-propanedinylbis (indenyl) titanium dimethyl (0.59 mmol) were sequentially added, and the temperature was raised to 30 ° C. The mixture was stirred at this temperature for 1 hour, and then propylene was continuously introduced into this so that the total pressure was maintained at 1.0 kg / cm ² G, and polymerization was carried out for 2.0 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polymer was dried. As a result, 4.0 g of a polymer was obtained, and II was 96.

Example 5 500 ml of purified toluene in a sus autoclave with an internal volume of 1.5 L that had been sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the method (A) above was 0.07 mmo as Ti component.
1, and 1,3-propanedinylbis (indenyl) titanium dimethyl (0.68 mmol) were sequentially added, and the temperature was raised to 30 ° C. The mixture was stirred for 1 hour with this warm tail, and then propylene was continuously introduced into this so that the total pressure was maintained at 1.0 kg / cm ² G, and polymerization was carried out for 4.0 hours. After the reaction, the catalyst dried was decomposed with methanol, and the obtained polymer was dried. As a result, 8.2 g of a polymer was obtained, and II was 95.

Comparative Example 1 700 ml of purified hexane was added to an autoclave made of sus having an internal volume of 1.5 L, which was sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the method (A) was used as a Ti component in an amount of 0.05 mmo.
1, and triethylaluminum 0.49 mmol were sequentially added, and the temperature was raised to 30 ° C. The mixture was stirred at this temperature for 1 hour, and then propylene was continuously introduced into this so that the total pressure was maintained at 1.0 kg / cm ² G, and polymerization was carried out for 2.0 hours. After the reaction
The catalyst component was decomposed with methanol, and the obtained polymer was dried. As a result, 19.2 g of polymer was obtained, and II was 7
Was 5.

Comparative Example 2 700 ml of purified hexane was added to a sus autoclave with an internal volume of 1.5 L that had been sufficiently replaced with nitrogen, and the Mg compound-supported titanium-based solid component prepared by the above-mentioned method (A) was used as a Ti component at 0.06 mmo.
1 and 0.60 mmol of diethylaluminum chloride were sequentially added, and the temperature was raised to 30 ° C. The mixture was stirred at this temperature for 1 hour, and then propylene was continuously introduced into this so that the total pressure was maintained at 1.0 kg / cm ² G, and polymerization was carried out for 2.0 hours.
After the reaction, the catalyst component was decomposed with methanol, and the obtained polymer was dried. As a result, 9.2 g of a polymer was obtained,
The II was 60.

[Brief description of drawings]

FIG. 1 is a flow sheet illustrating the steps of the method of the present invention. FIG. 2 is a flow sheet for explaining the production process of the titanium-based solid component according to the present invention.

Claims (3)

[Claims] 1. (A) A titanium-based solid component supported on a Mg compound produced through the following reactions of steps I to III, and I. anhydrous magnesium dihalide, a general formula Ti (OR ¹ ) ₄
In ortho titanate represented and / or the general formula ^{R 2 O-Ti (OR 3} ) (OR 4) m consists polytitanic acid ester represented by OR ⁵ (wherein ^{R 1, R 2, R 3} , R ⁴ and R ⁵ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, m is a number of 2 to 20), and a saturated group having 1 to 20 carbon atoms or An unsaturated monohydric or polyhydric alcohol is mixed and dissolved in an inert hydrocarbon solvent to obtain (Component A). II. The (Component A) contains an aliphatic or aromatic group having 2 to 24 carbon atoms. A mono- or polycarboxylic acid ester (hereinafter referred to as an organic acid ester) of the general formula AlX _n R ⁸ _3-n (wherein X is Cl or Br, R ⁸ is a cycloalkyl group having 3 to 20 carbon atoms, and n is 0). To a number of 3), and an aluminum halide represented by the general formula SiX _l R ▲ ⁶ _4-l SiX
_p (OR ⁷ ) _4-p (wherein X is Cl or Br, R ⁶ and R ⁷ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, l or p Is 1 to 4
A component (hereinafter referred to as solid product (I)) consisting of a silicon halide represented by the general formula: III. TiX _q (OR ⁹ ) _4-q (wherein X is Cl or Br, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is 1 to 4) and is composed of titanium halide and / or vanadyl halide or vanadium halide represented by the general formula VOX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ) _4-t. (Component C) is reacted to obtain a solid (hereinafter referred to as a solid product (II)). (B) A titanium dialkyl compound having as a bidentate ligand a bridge-type compound in which two groups selected from an indenyl group and a partial hydride thereof are bonded via a lower alkyl group. A method for producing an olefin polymer, which comprises polymerizing an olefin. 2. The method according to claim 1, wherein the titanium dialkyl compound (B) is ethylenebis (indenyl) titanium dimethyl. 3. The (B) titanium dialkyl compound is 1,
The method according to claim 1, which is 3-propanedinylbis (indenyl) titanium dimethyl.