JP2736931B2 - Method for producing olefin polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer. More specifically, the present invention relates to a method for producing an olefin polymer having excellent transparency and stereoregularity using a novel titanium trichloride composition as a transition metal compound catalyst component.

[Conventional technology and its problems]

Crystalline olefin polymers such as crystalline polypropylene polymerize olefins using a so-called Ziegler-Natta catalyst comprising a transition metal compound of group IV to VI of the periodic table and an organometallic compound of a metal of group I to III. It is well known that various titanium trichloride compositions are widely used as a transition metal compound catalyst component.

However, the olefin polymer obtained using the conventional titanium trichloride composition is opaque, and improvement in transparency has been desired.

In order to solve this problem, the present inventors have already carried out a step of carrying out a polymerization treatment using a non-linear olefin such as allyltrimethylsilane, vinylcyclohexane, 3-methylbutene-1, and styrene during the production of a titanium trichloride composition. Proposal of a production technique of a specific titanium trichloride composition obtained by introduction (for example, JP-A-1-282203, JP-A-1-318010, JP-A-1-318011, JP-A-1-318012) In the following, these inventions may be referred to as prior inventions.
doing.

In the case of obtaining an olefin polymer by polymerizing an olefin using the titanium trichloride composition produced by the method of the prior invention, there is a problem in production as compared with the case of using a conventional titanium trichloride composition. Thus, it was possible to obtain a homogeneous olefin polymer having excellent transparency, but further improvement in stereoregularity was desired.

The present inventors have excellent studies on titanium trichloride compositions which are excellent in transparency and can produce an olefin polymer having significantly high stereoregularity.As a result, when producing a titanium trichloride composition similar to the prior application invention, In any process, a novel titanium trichloride composition obtained by reacting a polycarboxylic acid ester is found, and when the titanium trichloride composition is used as a transition metal compound catalyst component for producing an olefin polymer, The present invention was completed by knowing that the stereoregularity of the obtained olefin polymer was significantly improved.

As apparent from the above description, an object of the present invention is to provide a method for producing an olefin polymer having excellent transparency and stereoregularity using a novel titanium trichloride composition as a transition metal compound catalyst component. To offer.

[Means for Solving the Problems] The present invention has the following configurations.

(1) Olefin is polymerized using a catalyst comprising a titanium trichloride composition (III), an organoaluminum compound (A ₁ ) and, if necessary, an electron donor (B ₁ ) to produce an olefin polymer. In the method, titanium tetrachloride is reacted with an organoaluminum compound (A ₂ ) or a reaction product (I) of an organoaluminum compound (A ₂ ) and an ether (B ₂ ) as a titanium trichloride composition (III). The solid product (II) obtained by
Polymerization treatment with a non-linear olefin, or a linear olefin and a non-linear olefin, and further reacting an ether (B ₃ ) with an electron acceptor to obtain a titanium trichloride composition (III)
A process for producing an olefin polymer, which comprises using a titanium trichloride composition (III) obtained by reacting a polycarboxylic acid ester (B ₄ ) at least once in an optional step of obtaining the olefin polymer.

(2) As the non-linear olefin, the following formula: CH ₂ CHCH—R ¹ (wherein, R ¹ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and may contain carbon which may contain silicon. 2. The method according to the above item 1, wherein a saturated cyclic hydrocarbon monomer represented by the following formula (3) is used.

(3) As the non-linear olefin, the following formula: (Wherein, R ² represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon;
³ , R ⁴ and R ⁵ each represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ³ , R ⁴ and R ⁵ may be hydrogen. Good. (2) The method according to the above (1), wherein the branched olefin represented by the formula (1) is used.

(4) As the non-linear olefin, the following formula: (Where n is 0, 1 and m is 1 or 2,
R ⁶ represents a linear hydrocarbon group having 1 to 6 carbon atoms which may contain silicon; and R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. And when m is 2, each R ⁷ may be the same or different. 2. The method according to the above item 1, wherein the aromatic monomer represented by the formula (1) is used.

(5) Instead of titanium trichloride composition (III), a combination of titanium trichloride composition (III) and an organoaluminum compound is used, and an olefin is reacted with 0.01 g to 200 g per 1 g of titanium trichloride composition (III). 2. The method of claim 1 wherein the preactivated catalyst component is used.

 The configuration of the present invention will be described in detail below.

The titanium trichloride composition (III) used in the present invention is obtained by reacting titanium tetrachloride with an organoaluminum compound (A ₂ ) or a reaction product (I) of an organoaluminum compound (A ₂ ) with an ether (B ₂ ). The resulting solid product (II) is polymerized with a non-linear olefin, or a linear olefin and a non-linear olefin, and further reacted with ethers (B ₃ ) and an electron acceptor to obtain trichloride. A novel titanium trichloride composition (III) obtained by reacting a polycarboxylic acid ester (B ₄ ) one or more times in an optional step of obtaining the titanium composition (III).

The above polyvalent carboxylic acid ester (B ₄ ) may be reacted at any stage of each step of obtaining the titanium trichloride composition (III), but the reaction may be carried out at the time of forming the solid product (II). , Reaction after the formation of solid product (II), non-linear olefin, or reaction after polymerization of linear olefin and non-linear olefin, reaction during formation of final titanium trichloride composition (III) The method of performing the reaction or a method combining these reactions is a method suitable for further exerting the effects of the present invention.

Hereinafter, a method of reacting the polycarboxylic acid ester (B ₄ ) after the formation of the solid product (II) will be described.
The present invention is not limited to this embodiment.

First, titanium tetrachloride is reacted with the organoaluminum compound (A ₂ ) or the reaction product (I) of the organoaluminum aluminum compound (A ₂ ) with the ethers (B ₂ ) to obtain a solid product (II).

In order to obtain the reaction product (I), the reaction between the organoaluminum compound (A ₂ ) and the ethers (B ₂ ) is carried out in a solvent (D ₁ ) at −20 ° C. to 200 ° C., preferably at −10 ° C. 100
C. for 30 seconds to 5 hours.

The order of addition of (A ₂ ), (B ₂ ) and (D ₁ ) is not limited, and the amount ratio used is 0.1 mol to 8 mol, preferably 1 to 4 mol, of ethers per 1 mol of organic aluminum.
0.5 to 5 l, preferably 0.5 to 2 l, is suitable. As the solvent, an aliphatic hydrocarbon is preferable. Thus, the reaction product (I) is obtained. The reaction product (I) can be subjected to the next reaction in a liquid state (sometimes referred to as a reaction product liquid (I)) in which the reaction is completed without separation.

Next, the reaction between the reaction product (I) or the organoaluminum compound (A ₂ ) and titanium tetrachloride (C) is carried out at 0 to 200
C., preferably at 10 to 90.degree. C. for 5 minutes to 8 hours. It is preferable not to use a solvent, but an aliphatic or aromatic hydrocarbon can be used.

The mixing of (A ₂ ) or (I), (C) and the solvent may be performed in any order, and the mixing of the entire amount is preferably completed within 5 hours. The amount of each solvent used in the reaction is 0 to 3,000 ml with respect to 1 mol of titanium tetrachloride, and the organoaluminum compound (A ₂ ) or the reaction product (I) is
The ratio of the number of Al atoms in the (A ₂ ) or (I) to the number of Ti atoms in the titanium tetrachloride (Al / Ti) is 0.05 to 10, preferably
0.06 to 0.3.

After the completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and further washing with a solvent is repeated. Then, the obtained solid product (II) is suspended in the solvent and subjected to the next step. It may be used, or it may be further dried and taken out as a solid.

The solid product (II) is then reacted with a polycarboxylic acid ester (B ₄ ). The reaction is carried out with the solid product (II) 100
g, 0.1 g to 1,00 of polyvalent carboxylic acid ester (B ₄ )
The reaction is carried out using 0 g, preferably in the presence of 100 ml to 5,000 ml of the solvent (D ₂ ) at a temperature of 0 ° C. to 200 ° C. for about 10 minutes to 5 hours to obtain a solid product (II-A). After completion of the reaction, washing with a solvent is preferred.

Subsequently, the solid product (II-A) is polymerized with a non-linear olefin or a linear olefin and a non-linear olefin.

In the present invention, “polymerization treatment” refers to the solid product (II) or (II) under the condition that a linear olefin can be polymerized.
-A) to polymerize an olefin or a non-linear olefin by contacting with (A).

Here, as a method of performing a polymerization treatment with a non-linear olefin or a linear olefin and a non-linear olefin, a solid product (II-A) is suspended in a solvent (D ₃ ), and an organoaluminum compound (A ₃ ) And a method of adding a non-linear olefin or a linear olefin and a non-linear olefin to carry out polymerization treatment. Further, as described above, the reaction of the polycarboxylic acid ester (B ₄ ) can be carried out in an optional step. Therefore, when the reaction of (B ₄ ) is carried out after the polymerization step, The method includes: (1) adding a non-linear olefin, or a linear olefin and a non-linear olefin in any step of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride. (2) After completion of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride, a non-linear olefin, or a linear olefin; (3) a method of polymerizing the solid product (II) by adding a non-linear olefin, and (3) after completion of the reaction of the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride, separation by filtration. Or after separating and removing the liquid part by decantation,
There is a method in which the obtained solid product (II) is suspended in a solvent, and an organic aluminum compound (A ₃ ) and an olefin are further added to carry out a polymerization treatment.

In addition, the non-linear olefin, or the polymerization treatment with the linear olefin and the non-linear olefin may be a polymerization treatment with the non-linear olefin alone. It is preferable to carry out a polymerization treatment and subsequently a polymerization treatment with a non-linear olefin from the viewpoint of improving the polymerization operability when using the obtained titanium trichloride composition (III) and the homogeneity of the obtained olefin polymer. Is the way.

Further, the polymerization treatment may be carried out by using a linear olefin and a non-linear olefin at least once each as described above, or by adding a linear olefin after polymerization treatment of two or more times, for example, a non-linear olefin. It is also possible to carry out a polymerization treatment.

The non-linear olefin or the polymerization treatment with the linear olefin and the non-linear olefin is carried out by a solid product (II-
In the case where A) is carried out after being suspended in the solvent (D ₃ ), and in the case of the above (3), the solid product (II
-A) or (II) solvent for 100g (D ₃₎ 100ml~
5,000 ml, organic aluminum compound (A ₃ ) 0.5 g to 5,000 g
Was added 1 minute to 10 hours at a reaction temperature of 0 ° C. to 90 ° C., the reaction pressure under conditions of atmospheric pressure ^{(0kgf / cm 2 G~10kgf / cm} 2 G, the solid product (II-A) or (II ) 0.1 g to 100 kg of linear olefin and 0.01 g to 100 k of non-linear olefin per 100 g
g, in the case of non-linear olefin homopolymerization treatment in the final titanium trichloride composition (III), so that the content of the non-linear olefin polymer is 0.01% by weight to 99% by weight,
When a linear olefin and a non-linear olefin are used, the content of the linear olefin polymer block is 0.1%.
The polymerization is carried out so that the content of the non-linear olefin polymer block becomes 0.01 to 49.5% by weight.

When the content of the non-linear olefin polymer is less than 0.01% by weight, the effect of improving the transparency and stereoregularity of the olefin polymer produced using the obtained titanium trichloride composition (III) is insufficient. If it exceeds the above range, the effect is not significantly improved, which is disadvantageous in terms of operation and economy.

In addition, as described above, the polymerization treatment is preferably performed not only with a non-linear olefin, but also with a linear olefin,
In this case, the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is 98/2 or less in consideration of the balance between the effect of improving operability and the effect of improving the quality of the obtained olefin polymer. Is preferred.

In the case where the polymerization treatment is carried out with an olefin by the above methods (1) and (2), the reaction temperature is 0 ° C. to 90 ° C. for 1 minute to 10 hours in any of the linear olefins and the non-linear olefins. , The reaction pressure is atmospheric pressure (0kgf / c
m ² G) to 10 kgf / cm ² G, the solid product (II-
0.1 g to 10 g of linear olefin per 100 g of A) or (II)
0 kg, and 0.01 g to 100 kg of non-linear olefin,
In the case of the non-linear olefin homopolymerization treatment in the final titanium trichloride composition (III), the content of the non-linear olefin polymer is from 0.01% by weight to 99% by weight. When using a non-linear olefin, the content of the linear olefin polymer block is from 0.1% by weight to 49.
5% by weight, non-linear olefin polymer block content
The polymerization is carried out so that the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is from 0.01 to 49.5% by weight, and 98/2 or less.

In any of the above-mentioned polymerization treatments, after the completion of the polymerization treatment in each stage with the linear olefin or the non-linear olefin, the reaction mixture can be used as it is in the next polymerization treatment. Further, the coexisting solvent, unreacted linear or non-linear olefin, and the organic aluminum compound are removed by filtration or decantation, etc. It may be used in a polymerization treatment with an olefin or a linear olefin.

The solvent used at the time of the polymerization treatment is preferably an aliphatic hydrocarbon, and the organoaluminum compound (A ₃ ) may be one used for obtaining the reaction product (I) or an ether (B
It may be the same as that used for the reaction with titanium tetrachloride directly without reacting with ₂ ) or a different one.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and further, washing is repeated with a solvent. Then, the obtained solid product subjected to polymerization treatment (hereinafter referred to as solid product (II-B) May be used in the next step as it is suspended in the solvent, or may be further dried and taken out as a solid.

The solid product (II-B) is then which is reacted ethers and (B ₃₎ an electron acceptor and (F). This reaction can be carried out without using a solvent, but the use of an aliphatic hydrocarbon gives better results.

The amount used is based on 100 g of the solid product (II-B).
(B ₃₎ 0.1g~1,000g, preferably 0.5g~200g, (F)
0.1 g to 1,000 g, preferably 0.2 g to 500 g, solvent 0 to 3,000 m
l, preferably 100-1,000 ml. As a reaction method, a method of simultaneously reacting an ether (B ₃ ) and an electron acceptor (F) with a solid product (II-B), (II-B)
After reacting the (F) to B), a method of reacting (B _3), after reaction (B ₃₎ to (II-B), a method of reacting (F), and (B ₃₎ After reacting (F),
There is a method of reacting (II-B), but any method may be used.

The reaction conditions are, in the above method, 40 ° C.
It is desirable to carry out the reaction at 200 ° C., preferably 50 ° C. to 100 ° C. for 30 seconds to 5 hours. In the method, the reaction between (II-B) and (B ₃ ) is carried out at 0 ° C. to 50 ° C. for 1 minute to 3 hours. After the reaction, (F) is reacted under the same conditions as described above.

In another method, (B ₃ ) and (F) are kept at 10 ° C to 100 ° C.
After reacting at 30 ° C for 30 minutes to 2 hours, cool to 40 ° C or less,
After adding (II-B), the reaction is carried out under the same conditions as described above.

The solid product (II-B), (B 3), and after the liquid portion was separated and removed by the completion of the reaction after filtration or decantation (F), repeatedly washed with additional solvent, trichloride used in the present invention A titanium composition (III) is obtained.

As described above, the reaction of the polyvalent carboxylic acid ester (B ₄ ) during the production of the titanium trichloride composition (III) is not limited to the above-described reaction with the solid product (II) but may be carried out in various other forms. The reaction can be performed at any stage during the production of the titanium trichloride composition (III).

As the organoaluminum compounds (A ₂ ) to (A ₃ ) used in the production of the titanium trichloride composition (III) used in the present invention, the general formula is AlR ⁸ _p R ⁹ _{p ′} X _{3- (p + p ′). )} (wherein, R ^8,
R ⁹ represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and p and p ′ represent any numbers of 0 <p + p ′ ≦ 3. The organic aluminum compound represented by the formula (1) is used.

Specific examples thereof include trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
Trialkyl aluminums such as tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-hexylaluminum, tri2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and diethyl Dialkylaluminum monohalides such as aluminum monochloride, di-n-propylaluminum monochloride, dii-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum monoiodide, and dialkyl such as diethylaluminum hydride Alkyl such as aluminum hydrides, methyl aluminum sesquichloride, ethyl aluminum sesquichloride Monoalkylaluminum dihalides such as luminium sesquihalides, ethylaluminum dichloride and i-butylaluminum dichloride; and alkoxyalkylaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can also be used. . These organoaluminum compounds can be used as a mixture of two or more kinds.

Specific examples of ethers for use in the production of titanium trichloride (III) used in the present invention (B ₂₎ and (B _3), diethyl ether, di-n- propyl ether, di-n- butyl ether, diisoamyl ether, di Examples include n-pentyl ether, di-n-hexyl ether, diisohexyl ether, di-n-octyl ether, diisooctyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran and the like. These ethers can be used as a mixture.

The ether (B ₂ ) for obtaining the reaction product (I) and the (B ₃ ) reacted with the solid product (II-B) may be the same or different.

Specific examples of the polycarboxylic acid ester (B ₄ ) used in the present invention include diethyl succinate, dibutyl succinate,
Diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, monooctyl maleate , Dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citrate, and the like. ,
Diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, alicyclic polycarboxylic acid esters such as diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, Monoisobutyl phthalate,
Diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-phthalate
Heptyl, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate,
Aromatic polycarboxylic acid esters such as diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and the like are used, and one or more kinds are used.

As the linear olefin used for the polymerization treatment, linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and octene-1 are used, and particularly, ethylene and propylene are preferably used.
One or more of these linear olefins are used.

The non-linear olefin used for the polymerization treatment is represented by the following formula: CH ₂ ＝ CH—R ¹ (wherein R ¹ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and may contain silicon. Represents a saturated ring hydrocarbon having 3 to 18 carbon atoms.) The following formula: (Wherein, R ² represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon;
³ , R ⁴ and R ⁵ each represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ³ , R ⁴ and R ⁵ may be hydrogen. Good. ) Represented by the following formula: (Where n is 0, 1 and m is 1 or 2,
R ⁶ represents a linear hydrocarbon group having 1 to 6 carbon atoms which may contain silicon; and R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. And when m is 2, each R ⁷ may be the same or different. ).

Specifically, examples of the saturated ring hydrocarbon monomer include vinylcyclopropane, vinylcyclobutane,
Vinylcycloalkanes such as vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methylvinylcyclohexane, 4-methylvinylcyclohexane, and vinylcycloheptane; allylcyclopentane; allylcyclohexane; In addition to allylcycloalkanes,
Cyclotrimethylenevinylsilane, cyclotomethylenemethylvinylsilane, cyclotetramethylenevinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, A saturated ring hydrocarbon having a silicon atom in a saturated cyclic structure such as cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, etc. Monomer, cyclobutyldimethylvinylsilane, cyclopent Dimethyl vinyl silane, cyclopentyl ethyl methyl vinyl silane, cyclopentyl diethyl vinyl silane, cyclohexyl vinyl silane, cyclohexyl dimethyl vinyl silane, cyclohexyl ethyl methyl vinyl silane, cyclobutyl dimethyl allyl silane, cyclopentyl dimethyl allyl silane, cyclohexyl methyl allyl silane, cyclohexyl diethyl allyl silane, cyclohexyl ethyl methyl allyl silane, cyclohexyl diethyl allyl silane, Examples thereof include a saturated cyclic hydrocarbon monomer containing a silicon atom in addition to a saturated cyclic structure such as 4-trimethylsilylvinylcyclohexane and 4-trimethylsilylallylcyclohexane.

Examples of the branched olefins include 3-methylbutene-1, 3-methylpentene-1, and 3-ethylpentene-1;
4-position branched olefins such as 1,4,4-dimethylpentene-1,4,4-diketylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethyl Alkenyl silanes such as methylsilane, allyltriethylsilane, allyltri-n-propylsilane, 3-butenyltriethylsilane, 3-butenyltriethylsilane, and diallylsilanes such as dimethyldiallylsilane, ethylmethyldiallylsilane, diethyldiallylsilane And the like.

Examples of the aromatic monomer include styrene, and derivatives thereof such as alkylstyrenes such as 0-methylstyrene and pt-butylstyrene, 2,4-dimethylstyrene, and 2,5-dimethylstyrene. Dialkylstyrenes, halogen-substituted styrenes such as 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p-fluorostyrene, p-trimethylsilylstyrene, m-triethylsilylstyrene , Trialkylsilylstyrenes such as p-ethyldimethylsilylstyrene, allyltoluenes such as 0-allyltoluene and p-allyltoluene, 2-allyl-p-xylene, 4-allyl-o-xylene, 5-allyl- Allyl xylenes such as m-xylene, vinyldimethylphenylsilane, vinylethylmethyl Alkenylphenylsilanes such as phenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane and allylethylmethylphenylsilane; and 4- (o-tolyl) -butene-1 and 1-vinylnaphthalene. One or more linear olefins are used.

The electron acceptor (F) used in the present invention has a periodic table III
Typified by halides of elements from the group VI to the group VI. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like. These can be used in combination, but the most preferred is titanium tetrachloride.

Solvents (D ₁ ), (D ₂ ) and (D ₃ ) include n
-Aliphatic hydrocarbons such as pentane, n-hexane, n-heptane, n-octane, isooctane, n-decane, carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, halogenated hydrocarbons such as tetrachloroethylene, benzene, Aromatic hydrocarbons such as naphthalene and derivatives thereof such as toluene, xylene, mesitylene, durene, ethylbenzene, isopropylbenzene,
Alkyl-substituted products such as ethylnaphthalene and 1-phenylnaphthalene, and halides such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene are shown, and these can be used in combination. is there.

The titanium trichloride composition (II
I) may be used in combination with an organoaluminum compound (A ₁ ) and, if necessary, an electron donor (B ₁ ) as a catalyst in a conventional manner for polymerization of olefins, or more preferably, by preliminarily reacting the olefins to react with the olefin. It is used for polymerization of olefins as a converted catalyst.

As the organoaluminum compound (A ₁ ) used for the polymerization of the olefin, the titanium trichloride composition (II
The same organoaluminum compound as (A ₂ ) or (A ₃ ) used in obtaining I) is used. As the electron donor (B ₁ ), a known electron donor (B ₁ ) used as a third component of the catalyst for the purpose of controlling stereoregularity during ordinary olefin polymerization is used. The electron donor (B ₁ ) is an organic compound having any of oxygen, nitrogen, sulfur and phosphorus, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines , Amides, urea or thioureas, isocyanates, azo compounds, phosphines,
Phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, silanols, Si
An organic silicon compound having a -OC bond or a mercapto group is exemplified.

As specific examples, (B ₂ ), (B ₃ ) and (B
₄ ) In addition to the compounds of ethers and polycarboxylic acid esters mentioned as examples of), methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol,
Alcohols such as glycerin, phenols, cresol, xylenol, ethylphenol, phenols such as naphthol, methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate;
I-propyl acetate, butyl formate, amyl acetate, n-acetate
Butyl, octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid 2
-Ethylhexyl, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphthoate 2-Ethylhexyl, monocarboxylic acid esters such as ethyl phenylacetate, aldehydes such as acetaldehyde, propionaldehyde and benzaldehyde, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid,
Valerian leaching, carboxylic acids such as benzoic acid, benzoic anhydride,
Acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and benzophenone, nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, 2,2,6,6′-tetramethylpiperidine, 2,2,5,5-
Amines such as tetramethylpyrrolidine, N, N, N ', N'-tetramethylethyldiamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N,
Amides such as N ', N', N "-pentamethyl-N'-β-dimethylaminomethylphosphoric triamide and octamethylpyrophosphoramide; ureas such as N, N, N ', N'-tetramethylurea , Isocyanates such as phenyl isocyanate, toluyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-
Phosphines such as octyl phosphine, triphenyl phosphine and triphenyl phosphine oxide, dimethyl phosphite, di-n-octyl phosphite, phosphites such as triethyl phosphite, tri n-butyl phosphite and triphenyl phosphite, ethyl diethyl Phosphinites such as phosphinite, ethylbutylphosphinite and phenyldiphenylphosphinite; thioethers such as diethylthioether, diphenylthioether and methylphenylthioether; thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol And thiophenols, silanols such as trimethylsilanol, triethylsilanol and triphenylsilanol, trimethylmethoxysilane, dimethyl Silane, diisopropyl dimethoxysilane, diphenyl dimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane,
Organosilicon compounds having a Si-OC bond such as ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrii-propoxysilane, vinyltriacetoxysilane, trimethylsilylbenzoate, triethylsilylbenzoate, etc. And mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, 3-mercaptopropyltrimethylsilane, 4-mercapto-
n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane,
Mercapto groups such as 3-mercaptopropyltriethylsilane, 1-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3-mercaptopropylethylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane, and 3-mercaptopropylmethyldiphenylsilane An organosilicon compound having the formula: mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyldiethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2
-Mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, diethoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane , An organic silicon compound having a Si-OC bond and a mercapto group such as 2-mercaptoethoxytrimethylsilane and 3-mercaptopropoxytrimethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-amino Propyldiethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-amido Ethylaminomethyltrimethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 2-aminoethylaminomethylbensiloxydimethylsilane, 3- [2- (2-aminoethylaminoethylaminopropyl] trimethoxysilane And organic silicon compounds having a Si—O—C bond and an amino group.

The type of polymerization of the olefin using the above-mentioned catalyst or the pre-activated catalyst is not limited, and the polymerization can be suitably performed not only in liquid phase polymerization such as slurry polymerization and bulk polymerization but also in gas phase polymerization. For slurry polymerization or bulk polymerization, titanium trichloride composition (III) and organoaluminum compound (A ₁ )
And a catalyst in which an electron donor (B ₁ ) is combined, if necessary, exhibits a sufficient effect, but in the case of gas phase polymerization,
It is desirable that the olefin be reacted and preactivated.

When performing gas phase polymerization following slurry polymerization or bulk polymerization, the same catalyst as the latter catalyst is used because the olefin reaction has already been performed during gas phase polymerization even if the catalyst initially used is the former. As a result, an excellent effect can be obtained.

The pre-activation is performed with respect to 1 g of the titanium trichloride composition (III), 0.005 g to 500 g of the organic aluminum compound, and 0 to 50 g of the solvent.
l, hydrogen 0-1,000ml and olefin 0.01g-5,000g
, Preferably from 0.01 g to 3,000 g. Temperature is 0 ° C ~ 1
The olefin is reacted at 00 ° C. for 1 minute to 20 hours, and 0.01 g to 2,000 g, preferably 0.01 g per 1 g of the titanium trichloride composition (III).
It is desirable to react from g to 200 g of olefin.

As the organoaluminum compound used for the preactivation, the same organoaluminum compound as (A ₁ ) used in the above-mentioned olefin polymerization may be used, and may be the same compound. It is also possible to coexist an electron donor during the preactivation.

The amount used is 0 to 2 per gram of titanium trichloride composition (III).
The weight is about 00 g, and specific examples thereof include the same electron donors as those described as (B ₁ ) used in the above-mentioned olefin polymerization.

The reaction of the olefin for preactivation can be performed in an aliphatic or aromatic hydrocarbon solvent, or in a liquefied olefin such as liquefied propylene or liquefied butene-1 without using a solvent. It can also be reacted. Furthermore, the reaction can be carried out in the presence of an olefin polymer or hydrogen in advance.

As the olefin used for the preactivation, ethylene,
Propylene, butene-1, pentene-1, hexene-
Linear olefins such as 1, heptene-1, octene-1, 4-methylpentene-1, 2-methylpentene-1, 3
And branched chain olefins such as -methylbutene-1 and styrene. These olefins may be the same as or different from the olefins to be polymerized.
It is also possible to use more than one type of olefin.

After the completion of the preactivation, the solvent, the organoaluminum compound, and the unreacted olefin are removed by distillation under reduced pressure or the like, and can be used as a dried powder in polymerization. Alternatively, 80 l / g of titanium trichloride composition (III) can be used. Can be used in the state of being suspended in a solvent that does not exceed the above range, and after removing the solvent, unreacted olefin and organoaluminum compound by filtration or decantation or the like, they can be dried and used as powders.

The polymerization of the olefin is carried out with the catalyst thus combined or with the preactivated catalyst. The amount of each catalyst component used in the polymerization of the olefin may be the same as the amount used in the preactivation described above. As the polymerization mode for polymerizing the olefin, as described above,
Slurry polymerization performed in a hydrocarbon solvent such as n-hexane, n-heptane, n-octane, benzene or triene, bulk polymerization performed in a liquefied olefin monomer such as liquefied propylene or liquefied butene-1, olefins such as ethylene and propylene In the gas phase, or a method of combining two or more of the above steps in a stepwise manner. In all cases, the polymerization temperature is from room temperature (20 ° C)
200 ° C, polymerization pressure is normal pressure (0Kg / cm ² G)-50Kg / cm ² G,
It is usually carried out for about 5 minutes to 20 hours.

During the polymerization, addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as in the conventional polymerization method.

Further, olefins to be subjected to polymerization include linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, and 4-methylpentene-.
Branched monoolefins such as 1,2-methyl-pentene-1; diolefins such as butadiene, isoprene and chloroprene; and not only homopolymerization of each of these but also other olefins. In combination, for example, propylene and ethylene, butene-1 and ethylene, propylene and butene-1 or propylene,
Copolymerization can be carried out by combining three components such as ethylene and butene-1, and block copolymerization can be carried out by changing the kind of olefin fed in multistage polymerization.

EXAMPLES Hereinafter, the present invention will be described with reference to examples. The definitions of terms used in Examples and Comparative Examples, and measurement methods are as follows.

TY: indicates the polymerization activity of the catalyst, and indicates the polymer yield per gram atom of titanium. (Unit: Kg / gram atom) II: Indicates the stereoregularity of the olefin polymer.

The olefin polymer is formed into a sheet having a thickness of about 1 mm at 200 ° C. using a press machine, and the sheet is cut into pieces each having a length of about 1 cm in length and width. The ratio of the remaining amount when extracted with boiling n-heptane for 6 hours using an extractor is shown. (Unit:% by weight) BD: Represents bulk specific gravity. (Unit: g / ml) MFR: Melt flow rate, according to JIS K 7210 Table 1 condition 14. (Unit: g / 10 minutes) Internal haze: Indicates the transparency inside the film excluding the influence of the surface. The olefin polymer is pressed at a temperature of 20
A film with a thickness of 150 μm at 0 ° C and a pressure of 200 kgf / cm ²
After applying liquid paraffin on both sides of the film, JIS K
Haze was measured according to 7105. (Unit:%) Example 1 (1) Production of titanium trichloride composition (III) 6 l of n-hexane, 5.0 mol of diethylaluminum monochloride (DEAC), and 12.0 mol of diisoamyl ether
Mix at 5 ° C for 1 minute, and react at the same temperature for 5 minutes. Reaction product liquid (I) (diisoamyl ether) / DEAC molar ratio
2.4) got.

Put 40 moles of titanium tetrachloride in a nitrogen-purged reactor,
Heat to 35 ° C and add the total amount of the reaction product liquid (I)
After dropping for 180 minutes, keep at the same temperature for 60 minutes, raise the temperature to 80 ° C, react for another 1 hour, cool to room temperature, remove the supernatant, add 20 l of n-hexane and decant. The operation of removing the liquid was repeated four times to obtain a solid product (II).

After suspending the entire amount of the solid product (II) in 10 l of toluene, 6.5 mol of diisobutyl phthalate was added and reacted at 80 ° C. for 1 hour. After the reaction is completed, the solid is
Times, followed by washing three times with n-hexane to obtain a solid product (II
-A) was obtained.

The whole amount of (II-A) was suspended in 30 l of n-hexane, and 400 g of diethyl aluminum monochloride was added.
1.6 kg of propylene was added at 30 ° C., and polymerization was performed at the same temperature for 1 hour. After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 30 l of n-hexane.

Subsequently, after adding 30 l of n-hexane and 400 g of diethylaluminum monochloride, the temperature was raised to 40 ° C., 2.0 kg of vinylcyclohexane was added, and polymerization was carried out at 40 ° C. for 2 hours. After completion of the reaction, the supernatant was removed and n-hexane was removed.
Add 30 l and remove the supernatant by decantation.
This was repeated twice to obtain a solid product (II-B) which was subjected to a multi-stage polymerization treatment with propylene-vinylcyclohexane.

In a state where the total amount of the solid product (II-B) was suspended in 9 l of n-hexane, 3.5 kg of titanium tetrachloride was added at room temperature to about 1 kg.
After adding for 0 minutes and reacting at 80 ° C. for 30 minutes, 1.6 kg of diisoamyl ether was further added and reacted at 80 ° C. for 1 hour. After completion of the reaction, the operation of removing the supernatant was repeated 5 times, and then dried under reduced pressure to obtain a titanium trichloride composition (III).

In the obtained titanium trichloride composition (III), the content of the propylene polymer block was 25.0% by weight, the content of the vinylcyclohexane polymer block was 25.0% by weight, and the titanium content was 12.0% by weight.

(2) Preparation of preactivated catalyst component After replacing a stainless steel reactor having an inner volume of 150 l with inclined blades with nitrogen gas, 100 l of n-hexane, 136 g of diethylaluminum monochloride, and the trichloride obtained in the above (1) were obtained. 1.5 kg of titanium composition (III) was added at room temperature. Subsequently, the temperature in the reactor was raised to 40 ° C, 2.0 kg of propylene was added, and 4
A preactivation treatment was performed at 0 ° C. for 1 hour (reaction of 1.0 g of propylene per 1 g of titanium trichloride composition (III)). After completion of the reaction, the reaction product was washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Polymerization of olefins L / D = 3 with a nitrogen-substituted 100 l internal volume stirrer
After 20 kg of the polypropylene powder obtained by a known method of MFR2.0 is added to the horizontal polymerization vessel of above, n-hexane is added to the preactivated catalyst component obtained in the above (2), and 4.0% by weight of n-hexane suspension is added. After forming a suspension, the suspension was 1.9 mg atom / hr in terms of Ti atom, and 30% by weight of diethyl aluminum monochloride and diisopropyldimethoxysilane in n-
The hexane solution was continuously supplied so that the molar ratio to Ti atoms was 7.0 and 0.5, respectively.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 1.1% by volume, and propylene was supplied so that the total pressure in the polymerization vessel was maintained at 23 kg / cm ² G.
The reaction was performed at 72 ° C. for 72 hours continuously. During the polymerization, the polymer was continuously withdrawn at 10 kg / hr from the polymerization vessel such that the level of the polymer in the polymerization vessel was 49% by volume. The extracted polymer was subsequently contacted with nitrogen gas containing 0.2% by volume of propylene oxide at 85 ° C. for 30 minutes,
The product was obtained as a polypropylene powder.

Comparative Example 1 (1) The solid product (II) in (1) of Example 1
Was reacted in the same manner as described above, except that the solid product (II) was used as a solid product (II-A) without reacting diisobutyl phthalate.

(2) A preactivated catalyst component was obtained in the same manner as in (2) of Example 1, except that the titanium trichloride composition obtained in (2) was used in place of the titanium trichloride composition (III). Was.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component.
Propylene was polymerized and post-treated in the same manner except that each catalyst component was supplied to the polymerization vessel such that the total pressure in the weight vessel was maintained at 23 kg / cm ² , to obtain polypropylene.

Comparative Example 2 In (1) of Comparative Example 1, the polymerization treatment of the solid product (II) with propylene was omitted, and the solid product (I)
A titanium trichloride composition was obtained in the same manner except that I) was used as a solid product (II-B). Thereafter, polypropylene was obtained in the same manner as in (2) and (3) of Comparative Example 1 using the titanium trichloride composition.

Example 2 (1) 4 l of n-heptane, 5.0 mol of diethyl aluminum monochloride, 9.0 mol of diisoamyl ether, di n
A reaction solution obtained by reacting 5.0 mol of -butyl ether at 18 ° C for 30 minutes was dropped into 27.5 mol of titanium tetrachloride at 40 ° C over 300 minutes, and then reacted at the same temperature for 1.5 hours.

Subsequently, 6.5 mol of di-n-butyl phthalate was added, and 65 ° C.
After elevating the temperature, the reaction was carried out for 1 hour, the supernatant was removed, 20 l of n-hexane was added, and the operation of removing by decantation was repeated 5 times to obtain a solid product (II-A). 1.9 kg of the solid product (II-A) was suspended in 40 l of n-hexane, 500 g of diethylaluminum monochloride was added, 0.6 kg of propylene was added at 30 ° C., and the mixture was reacted for 1 hour. Processing was performed.

After the elapse of the reaction time, the supernatant was removed, and n-hexane 20
The operation of adding l and removing by decantation was repeated twice. Subsequently, after adding 40 l of n-hexane and 500 g of diethylaluminum monochloride, 3.1 g of allyltrimethylsilane was added and reacted at 50 ° C. for 1 hour to carry out a second-stage polymerization treatment, and multistage polymerization with propylene-allyltrimethylsilane. The treatment gave a solid product (II-B).

After the reaction, the supernatant was removed, the operation of adding 20 l of n-hexane and removing by decantation was repeated twice, and the solid product (II-B) subjected to the polymerization treatment was treated with 7 l of n-hexane.
1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added and reacted at 60 ° C. for 3 hours.

After the reaction, remove the supernatant by decantation,
The operation of adding 20 l of n-hexane, stirring for 5 minutes and allowing to stand, removing the supernatant was repeated three times, and then dried under reduced pressure to obtain a titanium trichloride composition (III).

(2) A preactivated catalyst component was prepared in the same manner as in (2) of Example 1, except that the titanium trichloride composition (III) obtained in (1) above was used as the titanium trichloride composition (III). Obtained.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component.
Also, without supplying diisopropyldimethoxysilane, the polymerization of propylene and post-treatment were performed in the same manner except that the other catalyst components were supplied to the polymerization reactor so that the total pressure in the polymerization reactor maintained 23 kg / cm ² G, Polypropylene was obtained.

Comparative Example 3 A titanium trichloride composition was obtained in the same manner as in (1) of Example 2 except that the temperature was raised to 65 ° C without adding di-n-butyl phthalate. Thereafter, polypropylene was obtained in the same manner as in Example 2 except that the titanium trichloride composition was used instead of the titanium trichloride composition (III).

Example 3 (1) 27.0 mol of titanium tetrachloride was added to 12 l of n-hexane, cooled to 1 ° C., and 12.5 l of n-hexane containing 27.0 mol of diethylaluminum monochloride was further added at 1 ° C. for 4 hours. It was dropped. After the completion of the dropwise addition, the mixture was reacted at the same temperature for 15 minutes, then heated to 65 ° C. over 1 hour, and further reacted at the same temperature for 1 hour.

Next, the operation of removing the supernatant, adding 10 l of n-hexane and removing by decantation was repeated 5 times, and 1.8 kg of 5.7 kg of the obtained solid product (II) was suspended in 50 l of n-hexane. Then, 350 g of diethylaluminum monochloride was added, and 400 Nl of ethylene was further added at 30 ° C., followed by a polymerization treatment at the same temperature for 1 hour. Subsequently, the supernatant was removed by decantation, and the solid was washed with 50 l of n-hexane. After washing, 50 l of n-hexane and 350 g of diethylaluminum monochloride were added, and 3.0 kg of 3-methylbutene-1 was further added, followed by polymerization at 40 ° C. for 2 hours. After the polymerization treatment, the solid was washed with n-hexane to obtain a solid product (II-B).

Subsequently, the solid product (II-B) was suspended in 10 l of n-heptane, and 7.0 mol of diethyl butylmalonate was added.
The reaction was carried out at a temperature of 1 hour. After the reaction, the solid was washed four times with n-heptane. Further, the whole amount of the obtained solid was suspended in n-hexane 11, and 1.6 l of di-isoamyl ether was added thereto. After the suspension was stirred at 35 ° C. for 1 hour, the suspension was washed 5 times with 3 l of n-hexane to obtain a treated solid. The obtained treated solid was suspended in 6 l of a 40% by volume titanium tetrachloride n-hexane solution.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction is completed, use 20 l of n-hexane at a time,
The obtained solid was washed and dried under reduced pressure to obtain a titanium trichloride composition (III).

(2) A preactivated catalyst component was prepared in the same manner as in (2) of Example 1, except that the titanium trichloride composition (III) obtained in (1) above was used as the titanium trichloride composition (III). Obtained.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as a preactivated catalyst,
Also, in place of diisopropyldimethoxysilane, mercaptomethyltrimethylsilane was added at a molar ratio of 0.25 to Ti.
And propylene polymerization and post-treatment were carried out in the same manner except that each catalyst component was supplied to the polymerization reactor so that the total pressure in the polymerization reactor was 23 kg / cmG.

Comparative Example 4 (1) In Example 1 (1), the solid product (II-
A titanium trichloride composition was obtained in the same manner except that the step of reacting B) with diethyl butylmalonate was omitted.

(2) A preactivated catalyst component was obtained in the same manner as in (2) of Example 3, except that the titanium trichloride composition obtained in (2) was used in place of the titanium trichloride composition (III). Was.

(3) A polypropylene was obtained in the same manner as in (3) of Example 3, except that the preactivated catalyst component obtained in (2) was used as the preactivated catalyst component.

Example 4 (1) In Example 1 (1), the solid product (II)
, The fixation of diisobutyl phthalate to the reaction product is omitted, 5.0 mol of diisopropyl phthalate is added to the reaction product liquid (I), and the polymerization of the solid product (II-A) is replaced with propylene and vinylcyclohexane. And one-stage polymerization of styrene using 3.1 kg of styrene. Further, when the solid product (II-B) is reacted with titanium tetrachloride followed by diisoamyl ether, 1.0 mol of diisopropyl phthalate is added to the solid product (II-B). Titanium trichloride composition (III) was obtained in the same manner except that it was added and reacted with isoamyl ether.

(2) A preactivated catalyst component was obtained in the same manner as in (2) of Example 1, except that the titanium trichloride composition obtained in (2) was used in place of the titanium trichloride composition (III). Was.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and diethylene glycol dimethyl ether was used in place of diisopropyldimethoxysilane in a molar ratio to Ti.
It is supplied so as to be 0.01, and each catalyst component is supplied to the polymerization reactor so that the total pressure in the polymerization reactor is maintained at 23 kg / cm ² G. Further, the concentration in the gas phase of the polymerization reactor during the polymerization of propylene. Propylene-ethylene copolymerization and post-treatment were carried out in the same manner except that ethylene was supplied so as to maintain 0.2% by volume, to obtain a propylene-ethylene copolymer.

Comparative Example 5 (1) A titanium trichloride composition was obtained in the same manner as in (1) of Example 4, except that diisopropyl phthalate was not used.

(2) A preactivated catalyst component was obtained in the same manner as in (2) of Example 4, except that the titanium trichloride composition obtained in (2) was used in place of the titanium trichloride composition (III). Was.

(3) A propylene-ethylene copolymer was obtained in the same manner as in (3) of Example 4, except that the preactivated catalyst component obtained in (2) was used as the preactivated catalyst component.

The results of polymerization for the above Examples and Comparative Examples are shown in the table.

[Effect of the Invention] The main effect of the present invention is that a highly stereoregular olefin polymer having good transparency can be obtained with high polymerization activity.

 The effects of the present invention will be described more specifically.

The first effect of the present invention, when producing an olefin polymer,
That is, the production rate of the amorphous polymer is reduced, and a polymer having high stereoregularity is obtained. As is clear from the above-described embodiment,
For example, the boiling n-heptane extraction residual amount when a propylene homopolymer is obtained is 96.9% by weight to 98.7% by weight (Examples 1 to 3), and when the titanium trichloride composition of the prior application invention is used. Remarkably high in comparison.

Therefore, even without removing the atactic polymer, physical properties of the polymer, for example, rigidity, disadvantages such as lowering the thermal stability are eliminated, the step of removing the atactic polymer can be omitted, the polymer Can be simplified.

The second effect of the present invention is that an olefin polymer from which a molded article having good transparency can be obtained is produced, and has a significantly higher transparency than the conventionally known olefin polymer (Comparative Example 2). Thus, it can be widely used in application fields that have not been adopted in conventional olefin polymers.

A third effect of the present invention is that polymer particles having a good shape can be obtained with high polymerization activity. Since the polymer particles are nearly spherical and have a high bulk specific gravity (BD), the volume of the storage tank per polymer weight can be small, and the polymer production plant can be made compact and the polymer particles can be made compact. The trouble of clogging of the pipe due to the coagulation and the trouble of transportation due to the fine powder particles are eliminated, and a long-term stable operation is possible even in the gas phase polymerization method.

Also, the polymerization activity is increased by about 20% as compared with the case of using the titanium trichloride composition of the invention of the prior application, which contributes to the improvement of productivity.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram (flow sheet) for explaining the method of the present invention.

Claims (5)

(57) [Claims] 1. A titanium trichloride composition (III), an organoaluminum compound (A ₁ ) and, if necessary,
In a method for producing an olefin polymer by polymerizing an olefin using a catalyst comprising an electron donor (B ₁ ), an organoaluminum compound (A ₂ ) or an organoaluminum compound (A) is used as the titanium trichloride composition (III). ₂ )
Polymerizing ethers of (B ₂₎ with the reaction product solid product obtained by reacting titanium tetrachloride (I) of (II), in a non-linear olefin or a linear olefin and a non-linear olefin In the optional process of treating and then reacting the ethers (B ₃ ) with the electron acceptor to obtain the titanium trichloride composition (III), the polycarboxylic acid ester (B ₄ )
Titanium trichloride composition (II) obtained by reacting
A method for producing an olefin polymer, which comprises using I). 2. A non-linear olefin represented by the following formula: CH ₂ CHCH—R ¹ (wherein R ¹ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and may contain carbon which may contain silicon. 2. The method according to claim 1, wherein a saturated cyclic hydrocarbon monomer represented by the following formula (3) is used. 3. A non-linear olefin represented by the following formula: (Wherein, R ² represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon,
R ³ , R ⁴ and R ⁵ each represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ³ , R ⁴ and R ⁵
May be hydrogen. The method according to claim 1, wherein a branched olefin represented by the formula (1) is used. 4. A non-linear olefin represented by the following formula: (Wherein n is 0, 1, m is 1 or 2, R
⁶ represents a linear hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. When m is 2, each R ⁷ may be the same or different. The method according to claim 1, wherein the aromatic monomer represented by the formula (1) is used. 5. Titanium trichloride composition (III) is replaced by an organic aluminum compound in combination with titanium trichloride composition (III), and an olefin is added to the composition in an amount of 0.01 to 200 g per 1 g of titanium trichloride composition (III). 2. A process as claimed in claim 1, wherein the catalyst component is reacted and preactivated.