JPS6334167B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing olefin polymers. More specifically, the present invention relates to a method for producing an olefin polymer using a novel catalyst containing a titanium compound, a vanadium compound, and a zirconium compound.

It has been known to polymerize α-olefins such as ethylene using a so-called Ziegler catalyst consisting of a transition metal compound and an organoaluminium compound. For example, in Japanese Patent Publication No. 11269/1983,
A catalyst system consisting of an organoaluminum compound and a eutectic obtained by reducing a mixture or reactant of tetravalent titanium halide and vanadium oxyalkoxide with an organoaluminum compound has been proposed. This catalyst system has extremely high catalytic activity, and the polymer obtained using this catalyst system has very large advantages in the production of polymers, such as a narrow particle size distribution and high bulk density.

However, the polymers obtained with this catalyst system have a narrow molecular weight distribution and are suitable for injection molding, but are not suitable for applications that require a wide molecular weight distribution such as extrusion molding or blow molding. Nakatsuta.

Therefore, the present inventors investigated a catalyst system that is advantageous for producing polymers with a wide molecular weight distribution, and as a result, in Japanese Patent Application No. 64,740/1983, the present inventors discovered that titanium compounds, vanadium compounds, and zirconium compounds were We proposed a catalyst system that combines a solid catalyst component obtained by reacting with a compound and an organoaluminum compound. This catalyst system is highly active and is capable of reacting with titanium compounds, vanadium compounds,
By reacting the zirconium compound and the aluminum compound by changing the quantitative ratio of each component, it has the advantage that the molecular weight distribution of the polymer obtained by one catalyst system can be easily adjusted. It's very useful.

In order to improve this catalyst system, the present inventors conducted further intensive studies and found that when a solid catalyst component was prepared using organoaluminum bromide as an organoaluminum compound, hydrogen was not present in the reaction zone during polymerization. In this case, the effect of controlling the molecular weight by hydrogen becomes very large, and it is possible to obtain a polymer of the desired molecular weight more easily without impairing the properties of the catalyst system obtained as explained above. Heading, we arrived at the present invention.

That is, the gist of the present invention is as follows: (A) a titanium compound selected from organic oxygenated compounds and halogenated compounds of titanium; (B) a vanadium compound selected from organic oxygenated compounds and halogenated compounds of vanadium; A solid catalyst component is separated from the reaction mixture obtained by reacting a zirconium compound selected from organic oxygenated compounds and halogenated compounds, and (D) an organoaluminium bromide compound, and this is combined with the organoaluminum compound. The present invention relates to a method for producing an olefin polymer, which comprises polymerizing olefin using a catalyst.

To explain the present invention in detail, the titanium compound, vanadium compound and zirconium compound used in the preparation of the solid catalyst component in the present invention are selected from organic oxygenated compounds and halogenated compounds of each metal. The term “organic oxygenated metal compound” here refers to at least one metal oxygen compound per molecule.
It means a compound that has organic group bonds in this order.
and at least one metal - oxygen - per molecule.
If it has an organic group bond, metal-oxygen-
It may also be a condensation compound with metal-type bonds.
Any organic group can be selected, but it generally has 1 to 20 carbon atoms, and more preferably a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, or an alkylaryl group. group, arylalkyl group, etc. are used. On the other hand, a metal halide compound means a compound having at least one metal-halogen bond per molecule. and at least 1 per molecule
If it has metal-halogen bonds,
It may also be a condensation compound having a metal-oxygen-metal type bond. As this halogen atom, fluorine, chlorine, bromine, and iodine can be used.
Among these, it is most preferable to use bromine. Such organic oxygenated compounds and halogenated compounds have the general formula [M _e O _a (OR) _b X _c ] _d (in the formula,
R represents the above organic group, X represents the above halogen atom, and M _e is titanium, vanadium or zirconium. a is 0≦a≦1, b, c is 0≦b≦
5,0≦c≦5, and a×2+b+c is equal to the valence of each metal. d is an integer satisfying 1≦d≦6. ) are most preferred.

Therefore, a titanium compound has the general formula [TiO _a1 (OR ¹ ) b ¹ X ¹ c ¹ ] d ¹ (wherein a ¹ , b ¹ , c ₁ are 0
≦a ¹ ≦1, 0≦b ¹ ≦4, 0≦c ¹ ≦4 and a ¹ ×2 + b ¹
+c ¹ = 4, and d ¹ is 1≦d ¹ ≦6
is an integer. R ₁ is an alkyl group having 1 to 20 carbon atoms,
Represents a cycloalkyl group, aryl group, alkylaryl group or arylalkyl group. X ¹ represents a halogen atom. ) is preferable, but among these, tetravalent titanium compounds represented by the general formula Ti
(OR ² ) a ² X _4-a2 (where a ² is a number satisfying 0≦a ² ≦4,
R ² and X ² are the same as R ¹ and X ¹ above. ) is particularly preferred. Bromine is the most preferred halogen atom. These compounds include alkoxides such as Ti(OC ₂ H ₅ ) ₄ ,
Ti(O-n-C ₄ H ₉ ) ₄ ; Phenoxide e.g. Ti
(OC ₆ H ₅ ) ₄ ; oxyalkoxide e.g. TiO
(OC ₂ H ₅ ) ₂ ; condensed alkoxides such as Ti ₂ O(O
-i-C ₃ H ₇ ) ₆ ; Tetrahalide such as TiCl ₄ ,
TiBr ₄ ; oxyhalides such as TiOBr ₂ and halogenated alkoxides such as Ti(OC ₂ H ₅ ) ₂ Br ₂ ,
Examples include Ti(O-n-C ₄ H ₉ ) ₃ Br. Complexes of these compounds with various Lewis bases, e.g.
TiBr _4.2 (butyl ether), TiBr ₃ (O-
nC ₄ H ₉ )・ethyl acetate, etc. may also be used.
Compounds containing several different organic groups or halogen atoms can also be used, as well as several different titanium compounds.

As a vanadium compound, the general formula [VO _a3
^{( OR 3 ) b 3 _ _ _ _ _ 3} ×2
+b ³ +c ³ is a number equal to the valence of vanadium, and a ³ is an integer satisfying 1≦d ³ ≦6. ^R3 ,
X ₃ is the same as R ¹ and X ¹ . ) A tetravalent or pentavalent vanadium compound represented by the formula VO(OR ⁴ ) a ⁴ X ⁴ _3-a4 (wherein a ⁴ is 0≦
The number a ⁴ ≦ 3, R ⁴ and X ⁴ are the same as R ¹ and X ¹ . ), and a pentavalent vanadium compound represented by the general formula V
^{( OR 4} ₎ ^{b 4}
R ⁴ and X ⁴ are the same as above. ) is particularly preferred. Bromine is the most preferred halogen atom. These compounds include oxyalkoxides such as VO(O-n
-C ₄ H ₉ ) ₃ , VO(OC ₂ H ₅ ) ₃ ; Oxychloride e.g. VOCl ₃ , VOBr ₃ ; Oxyphenoxide e.g. VO(OC ₆ H ₅ ) ₃ ; Oxyalkoxychloride e.g. VO(OC ₂ H ₅ ) ₂ Br, VO(O-n-
C ₄ H ₉ ) ₂ Br, VO(O—n—C ₄ H ₉ )Br ₂ ; Tetrahalide, for example, VBr ₄ and the like. VBr ₄・2
Complexes with various Lewis bases such as (butyl ether) may also be used. It is also possible to use compounds containing several different organic groups or halogen atoms,
It is also possible to use several different vanadium compounds.

Zirconium compounds have the general formula [ZrO _a5
^{( OR 5 ) b 5 _ _ _}
1, 0≦b ⁵ ≦4, 0≦c ⁵ ≦4 and a ⁵ ×2 + b ⁵ + c ⁵ =
4, and d ⁵ is an integer satisfying 1≦d ⁵ ≦6. R ⁵ and X ⁵ are the same as R ¹ and X ¹ . ) ^A tetravalent zirconium compound represented by ^the general ^formula _Zr ⁽ OR ^{6 )} a ⁶ A tetravalent zirconium compound represented by R ¹ and X ¹ is particularly preferred. Bromine is the most preferred halogen atom.
These compounds include alkoxides such as
Zr(O-n-C ₄ H ₉ ) ₄ , Zr(OC ₂ H ₅ ) ₄ ; Phenoxides such as Zr(OC ₆ H ₅ ) ₄ ; Alkoxychlorides such as Zr(O-n-C ₄ H ₉ ) ₃ Br, Zr(O-n-
C ₄ H ₉ ) ₂ Br ₂ ; Tetrahalide e.g. ZrCl ₄ ,
ZrBr ₄ ; oxyhalide such as ZrOBr ₂ (this compound is usually used in the form of ZrOBr _{2.8H 2} O).
etc. ZrBr ₄・2 (ethyl acetate)
You may use the complex with various Lewis bases, such as.
It is also possible to use several different organic groups or compounds containing halogen atoms, as well as several different zirconium compounds.

Thus, the solid catalyst component in the present invention can be obtained by reacting the aforementioned titanium compound, vanadium compound, and zirconium compound with an organoaluminium bromide compound. Such organic aluminum bromide compounds have the general formula
An aluminum compound represented by AlR ⁷ _o Br _3-o (wherein R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and n is a number of 0<n<3) It is preferable to use Furthermore, R ⁷ is preferably selected from an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group and an alkylaryl group. These compounds include Al( _CH3 )
Br ₂ , Al (C ₂ H ₅ ) Br ₂ , Al (i-C ₄ H ₉ ) Br ₂ , Al
(n- _C8H17 ) _Br2 ,Al _{( C2H5} ) _{2Br ,} Al
(C ₂ H ₅ ) ₂ Br, (CH ₃ ) _1.5 AlBr _1.5 , (C ₂ H ₅ ) _1.5 AlBr _1.5
etc. Several different organoaluminum bromide compounds can be used, and organoaluminum bromide compounds containing several different organic groups can be used. Further, an organoaluminum bromide compound and an organoaluminum compound not containing bromine may be used together, or aluminum tribromide and an organoaluminum bromide compound may be used together. Among these, Al(C ₂ H ₅ ) Br ₂ , Al
Preference is given to using organoaluminium dibromides such as ( _CH3 ) _Br2 .

The reaction may be carried out by adding and mixing each component in any order and allowing the reaction to occur. For example, a titanium compound, a vanadium compound, and a zirconium compound are mixed, and an organoaluminum bromide compound is added to the resulting mixture or reactant to react. Specifically, first, a titanium compound, a vanadium compound, and a zirconium compound are added and mixed. In this case, the order of addition of each compound can be arbitrarily selected. After mixing, a reaction may occur between each compound. The temperature conditions during addition are not particularly limited, and range from 0℃ to 200℃.
℃, usually normal temperature, and the pressure conditions are not particularly limited, and usually normal pressure may be used. Although the mixing may be performed in the presence or absence of a diluent, it is preferable that the mixture is in a liquid state (it may be in a slurry state). Therefore, if the compound itself is not liquid under the mixing conditions, or if the amount of liquid compound is insufficient, it is preferable to add a diluent. As the diluent, all common inert hydrocarbon solvents can be used, but alkanes having 6 to 20 carbon atoms, cycloalkanes and aromatic hydrocarbons are preferably used. These compounds include hexane, heptane, cyclohexane, benzene, toluene,
Examples include xylene. It is also possible to use polar solvents. Examples of these solvents include ethylene dichloride, alcohols having 1 to 8 carbon atoms, carboxylic acid esters, ethers,
Examples include pyridine. titanium, vanadium,
The addition of each zirconium compound may be carried out as a solution in the above-mentioned polar solvent and inert hydrocarbon solvent.

Next, the mixture or reactant of the titanium compound, vanadium compound, and zirconium compound obtained as described above is reacted with an organoaluminium bromide compound to prepare a solid catalyst component. The reaction with the organoaluminum bromide compound is preferably carried out in the presence of an inert solvent, even if the mixture or reactant obtained as described above is sufficiently liquid in the absence of a diluent. Among the inert solvents exemplified above as diluents, inert hydrocarbon solvents are usually used. When a polar solvent is used during mixing, this polar solvent may be removed by distillation under reduced pressure or other methods prior to the reaction with the organoaluminium bromide compound, or the polar solvent may be removed as it is without being removed. A reaction with an aluminum compound may also be performed.

In the reaction with an organoaluminium bromide compound, the organoaluminium bromide compound is added to a mixture or reactant of a titanium compound, a vanadium compound, and a zirconium compound to which an inert solvent has been added, preferably at room temperature to 200°C, more preferably at 50°C to The reaction can be carried out at a temperature of 150°C, and since an inert solid is obtained in an inert solvent, the solid is separated and washed with an inert solvent.

In the second method, after adding and mixing a vanadium compound and a zirconium compound, an organoaluminum bromide compound is added in the presence of an inert solvent to carry out the reaction, or subsequently a titanium compound is added to carry out the reaction. The reaction conditions were according to the method described above.

The amount of each compound to be used is the total sum t expressed in gram equivalents of each metal in the titanium compound, vanadium compound, and zirconium compound, and the amount of the titanium compound,
The ratio of the sum u expressed in gram equivalents of each halogen atom in the vanadium compound, zirconium compound, and organoaluminum bromide compound, that is, u/t
However, it is preferable to select such that u/t>0.6, preferably u/t>1. Here, the gram equivalent is
Gram equivalent = amount defined as gram atom of element/valence of element. When u/t>0.6, there is an advantage that it is particularly easy to produce a polymer with a wide molecular weight distribution. There is no particular restriction on the upper limit of the value of u/t, but a value up to about 10 is usually sufficient. In addition, when the usage amount of halogen atoms represented by u includes the usage amount of other halogens in addition to bromine, the ratio of bromine to other halogens, that is,
It is preferable that the molar ratio of hydrogen to other halogens is 10 or more. Further, it is preferable that the amount of each metal, titanium, vanadium, and zirconium, expressed in gram atoms, be selected so as to satisfy the following formula. That is, 0.1×<Zr/Ti<10, 0.01<(Zr+Ti)/V<
100 More preferably 0.2<Zr/Ti<8, 0.05<(Zr
+Ti)/V<10 (In the formula, Ti, V and Zr are the amounts of titanium, vanadium and zirconium atoms in each compound, respectively, expressed in gram atoms.)
When the value of Zr/Ti is within the above range, this catalyst system makes it particularly easy to produce polymers with a wide molecular weight distribution, and when the value of (Zr+Ti)/V is within the above range, the catalyst system This has the advantage that the polymerization activity of the system is particularly high.

Next, as the organoaluminum compound used ^as a cocatalyst, for example, the general formula AlR ⁸ _k X ⁸ _3-k (wherein R ⁸ represents an alkyl group, aryl group or cycloalkyl group, k is 1
- indicates the number of 3. ) can be mentioned. Specifically, trialkylaluminum such as triethylaluminum, tri-n-propylaluminum, and triisobutylaluminum is preferred.

The proportion of the hydrocarbon-insoluble solid and the organoaluminum compound used is usually within the range of 0.1 to 100, preferably 1 to 20, in terms of the atomic ratio of Al/(V+Ti+Zr).

The catalyst system thus prepared is used to polymerize olefins, and the olefins used in the method of the present invention include ethylene, propylene,
α of butene-1, pentene-1, octene-1, etc.
-There is olefin. Moreover, these olefins can also be mixed and copolymerized. In particular, the process of the invention is advantageous for the production of ethylene homopolymers or copolymers of ethylene containing up to 10% by weight, preferably up to 5% by weight of other α-olefins. The polymerization reaction can be carried out by solution polymerization or slurry polymerization carried out in an inert solvent, or by gas phase polymerization carried out in the absence of a solvent.
This is usually carried out by supplying the olefin or olefin mixture and maintaining it at a predetermined temperature and pressure in the presence of an inert solvent. Examples of inert solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane and cyclohexane;
Aromatic hydrocarbons such as benzene and toluene are used. The polymerization reaction is usually carried out at a temperature of from room temperature to 200°C and a pressure of from normal pressure to 100 atmospheres.

Further, in the method of the present invention, when hydrogen is present in the polymerization reaction zone, the effect of controlling the molecular weight by hydrogen is very large, and a polymer having a desired molecular weight can be easily obtained. The amount of hydrogen to be present varies depending on the polymerization conditions, the desired molecular weight of the olefin polymer, etc., and therefore it is necessary to adjust the amount of hydrogen introduced accordingly. For example, at a polymerization temperature of 70℃, the melt index is 0.3~
When producing a 0.05% polymer, it is sufficient to add approximately 30 to 150 mol% of hydrogen to ethylene.

According to the method of the present invention as described above, in addition to the advantage that the catalyst system has high activity, it is possible to obtain the advantage that the catalyst system is highly active. This provides the advantage that the molecular weight distribution of the resulting polymer can be easily controlled. An olefin polymer having a wide molecular weight distribution and excellent moldability in extrusion molding and blow molding can be obtained. In addition, the effect of controlling the molecular weight by hydrogen becomes very large, and it is easier to produce a polymer of the desired molecular weight with a smaller amount of hydrogen than before, without impairing the properties of the catalyst system obtained by the previous invention. can be obtained.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In the examples, the polymerization activity K of the catalyst was expressed as K=(g polymer)/(g·catalyst) (hr) (Kg/cm ² olefin pressure). In addition, the melt index is
2.16Kg at 190℃ based on ASTM・D・1238・57T
It was measured by load and expressed in MI. Furthermore, the flow rate ratio (hereinafter abbreviated as FR), which is a measure of molecular weight distribution, is a value that indicates the dependence of melt viscosity on shear stress, and is a value specified by ASTM.
According to D・1238・57T, it is expressed as the ratio of melt index measured at shear stress of 10 ⁶ dyne/cm ² and 10 ⁵ dyne/cm ² , and the larger the FR, the broader the molecular weight distribution, and the smaller the molecular weight distribution. If so, it is considered narrow.

Examples 1 to 5 (1) Production of catalyst Zirconium tetra-normal butoxide (10 ml of normal hexane) was dissolved in titanium tetra-normal butoxide, vanadyl tri-normal butoxide, and normal hexane in the proportions shown in Table 1. (dissolved at a ratio of 10 mmol of zirconium tetra-normal butoxide) and normal hexane to form a homogeneous solution. then 60
Ethylaluminum dibromide in the amount shown in Table 1 was added dropwise at 65° C. in the form of a 3.5 mol/n-hexane solution, and the mixture was stirred at 65° C. for 1 hour. The generated precipitate was washed with n-hexane and dried to obtain a catalyst powder.

In Table 1, Ti(O-n-Bu) ₄ , VO(O-n-
Bu) ₃ and Zr(O-n-Bu) ₄ represent titanium tetra-normal butoxide, vanadyl tri-normal butoxide, and zirconium tetra-normal butoxide, respectively, and EtAlBr ₂ represents ethylaluminum dibromide.

(2) Polymerization of ethylene 1. 500 c.c. of n-hexane was placed in an autoclave and 20 mg of the above catalyst powder was charged therein. After raising the temperature to 70℃,
Hydrogen was introduced to the predetermined pressure shown in Table 1, and 0.4 mmol of triisobutylaluminum was introduced together with ethylene to bring the total pressure to 15 Kg/cm ³ . Ethylene absorption is seen as ethylene is introduced, but when the total pressure is reduced to 15 kg/
Ethylene was additionally introduced to maintain the temperature at cm ² , and 1 hour later, the polymerization was stopped by pressurizing ethanol. The results obtained are shown in Table 1.

In the table, the amount of normal hexane in the zirconium tetrabutoxide solution,
and the total amount of normal hexane added separately.

Example 6 The same procedure as in Example 1 was carried out, except that commercially available zirconium normal butyrate containing 14 to 16% by weight of normal butanol was used as the zirconium compound, and the amounts of each compound used were as shown in Table 1. A catalyst powder was obtained.

Ethylene polymerization was carried out in exactly the same manner as in Example 1, except that 20 mg of this catalyst powder was used and hydrogen was introduced up to 6.1 Kg/cm ² . The results are shown in Table 1.

Examples 7-9 Various titanium, vanadium, zirconium compounds and n-hexane were mixed in the proportions shown in Table 1.

In Examples 8 and 9, it was observed that heat generation and a change in color tone occurred simultaneously with mixing, indicating that a reaction was occurring between the respective compounds.

After mixing, the mixture was stirred at 60°C for 30 minutes, and then the aluminum compound shown in Table 1 was added dropwise at 60°C in the form of a 3.5 mol/n-hexane solution, and the mixture was stirred at 65°C for 1 hour. The generated precipitate was washed with n-hexane and dried to obtain a catalyst powder.

Using 20 mg of this powder, ethylene polymerization was carried out in exactly the same manner as in Example 1, except that hydrogen was introduced to the pressure shown in Table 1. The results are shown in Table 1.

In Table 1, TiCl ₄ and ZrBr ₄ are titanium tetrachloride and
Represents zirconium tetrabromide. Also, Et ₃ Al ₂ Br ₃
represents ethylaluminum sesquibromide.

Example 10 When introducing and adding ethylene in the polymerization of ethylene in Example 4, butene-1 was mixed, and the molar ratio of butene-1/ethylene in the gas phase during the polymerization reaction was
Copolymerization of ethylene and butene-1 was carried out in exactly the same manner except that the copolymerization ratio was 0.009. The obtained results are shown in Table 1, and the obtained polymer was an ethylene-butene-1 copolymer containing 0.1 mol% of butene-1 units.

Comparative Example 1 A solid catalyst component was produced in the same manner as in Example 1, except that 330 mmol of ethylaluminum dichloride was used instead of 315 mmol of ethylaluminum dipromide.

Using this catalyst, polymerization was carried out in the same manner as in Example 1 except that the hydrogen pressure was 8.5 Kg/cm ² .
221 g of polymer with MI=0.10 and FR71 was obtained. K=
It was 1700.

Thus, in the catalyst system using organoaluminum chloride, the effect of controlling molecular weight by H ₂ is smaller than in the catalyst system using organoaluminum bromide.

Comparative Example 2 A solid catalyst component was produced in the same manner as in Example 2, except that 338 mmol of ethylaluminum dichloride was used instead of 385 mmol of ethylaluminum dibromide.

Polymerization was carried out in exactly the same manner as in Example 2 using this catalyst.

As a result, the MI of the obtained polymer was very small at 0.014, and the catalyst system using organoaluminium chloride had a smaller molecular weight adjustment effect by H ₂ than the catalyst system using organoaluminum bromide. In addition, K
= 1300, FR was unmeasurable.

Comparative Example 3 A catalyst was produced in exactly the same manner as in Example 10, except that ethylaluminum dichloride was used instead of ethylaluminum dibromide, and the amount of hydrogen was varied from 6.5 Kg/cm ² to 9.3 Kg/cm ² Polymerization was carried out in the same manner as in Example 10 except that the amount was increased to
143 g of polymer with MI=0.07 and FR78 was obtained.

As described above, even in ethylene-1-butene copolymerization, the catalyst system using organoaluminum chloride has a smaller molecular weight adjustment effect by hydrogen than the catalyst system using organoaluminum bromide.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing one embodiment of the present invention.

【table】

Claims (1)

[Scope of Claims] 1 (A) A titanium compound selected from organic oxygenated compounds and halogenated compounds of titanium (B) A vanadium compound selected from organic oxygenated compounds and halogenated compounds of vanadium (C) Organic oxygen of zirconium A solid catalyst component is separated from the reaction mixture obtained by reacting a zirconium compound selected from halogenated compounds and halogenated compounds, and (D) an organoaluminium bromide compound, and a catalyst formed by combining this with the organoaluminum compound is prepared. 1. A method for producing an olefin polymer, comprising polymerizing an olefin using the method. 2. In the method described in claim 1,
The general formula for the organoaluminum bromide compound of (D) is
AlR ⁷ _o Br _3-o (wherein R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms,
n is a number satisfying 0<n<3. ) A method for producing an olefin polymer, comprising using a solid catalyst component obtained by reacting with a compound represented by: 3. In the method according to claim 1 or 2, a titanium compound, a vanadium compound,
Zirconium compounds and organoaluminium bromide compounds are represented by the formula u/t>0.6 (where u is a titanium compound, a vanadium compound,
The sum of each halogen atom in the zirconium compound and organoaluminum bromide compound is expressed in gram equivalent, and t is the sum of each metal atom in the titanium compound, vanadium compound, and zirconium compound expressed in gram equivalent. be. ) A method for producing an olefin polymer, characterized by using a solid catalyst component obtained by reacting with a satisfying amount of olefin polymer. 4. In the method according to any one of claims 1 to 3, a titanium compound, a vanadium compound, a zirconium compound, and an organoaluminum bromide compound are combined with the formula 0.1<Zr/Ti<10, 0.01<(Zr+Ti) /V<100 (In the formula, Ti, Zr, and V are the amounts of titanium, zirconium, and vanadium atoms in each compound expressed in gram atoms.) obtained by reaction using a satisfying amount. A method for producing an olefin polymer, characterized by using a solid catalyst component. 5. In the method according to any one of claims 1 to 4, a titanium compound, a vanadium compound, a zirconium compound, and an organoaluminum bromide compound are combined with the formula 0.2<Zr/Ti<8, 0.05<(Zr+Ti) /V<10 (In the formula, Ti, Zr, and V are the amounts of titanium, zirconium, and vanadium atoms in each compound expressed in gram atoms.) A method for producing an olefin polymer, characterized by using a solid catalyst component. 6. A method for producing an olefin polymer, which comprises polymerizing the olefin in the presence of hydrogen in the method according to any one of claims 1 to 5.