JPS6349684B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a highly crystalline olefin polymer with a wide molecular weight distribution. Specifically, the present invention relates to a method for producing a highly crystalline olefin polymer that uses a novel catalyst system, has high polymerization activity and stereoregularity, has a wide molecular weight distribution, and is excellent in hollow molding, extrusion molding, etc. Conventionally, for polymerization catalysts for olefins (particularly propylene), halides of transition metals from groups _b to _b of the periodic table (generally titanium trichloride) and metals or organometallic compounds from groups b to b of the periodic table have been used. It is well known that a catalyst system consisting of (generally diethylaluminum chloride) is suitable. In addition, in recent years, many studies have been conducted on supported catalysts in which transition metal compounds are supported on various carriers in order to increase the catalytic activity per transition metal. Catalyst systems consisting of the above components, a trialkylaluminium compound, and an organic acid ester are also known to be preferred for the polymerization of propylene. However, when producing olefin (especially propylene) polymers using these catalysts, the molecular weight distribution of the resulting polymers is not very wide. Therefore, in the fields of extrusion molding and hollow molding, high molding speeds cannot be obtained during molding, resulting in a decrease in the production capacity of processing machines, and the resulting molded products have rough skin, uneven thickness, etc., and their commercial value is substantially reduced. This brings about disadvantages such as being poor. Therefore, in the field of extrusion molding and hollow molding, it is important to have (1) high catalytic activity, (2) high stereoregularity of the obtained polymer, and (3) wide molecular weight distribution of the obtained polymer. Developing a catalyst that satisfies both of these requirements would be extremely advantageous industrially in the production of highly crystalline olefin polymers. By the way, in the production of ethylene polymer,
Many catalyst systems that produce polymers with a wide molecular weight distribution have been proposed so far, but α
- In the production of olefin polymers, high activity,
A catalyst system that produces polymers with high stereoregularity and a wide molecular weight distribution has not yet been found. From the above viewpoint, the present inventors conducted intensive research on a method for producing a highly crystalline olefin polymer with a wide molecular weight distribution that is industrially advantageous. As a result, the present inventors discovered that a novel catalyst for highly crystalline olefin polymerization which has sufficiently high activity and stereoregularity from an industrial standpoint and has a wide molecular weight distribution of the produced polymer has been achieved, and the present invention has been achieved. That is, the present invention provides (A) titanium trichloride (B) general formula R ¹ _3-(n+o) AlY _n X _o (where Y is NR ² R ³ ,
selected from the group consisting of SR ⁴ and PR ⁵ R ⁶ , R ¹ ~
R ⁶ represents hydrogen and/or an alkyl group, alkenyl group, alkynyl group, alicyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 18 carbon atoms.
X represents halogen. Also, m and n are 0.1≦m≦0.9 and 0≦, respectively.
It is a number expressed by n≦1.9, 0.1≦m+n≦2. ) an organoaluminum compound represented by
and (C) using a catalyst system consisting of an electron-donating compound to
The present invention relates to a method for producing a highly crystalline olefin polymer with a wide molecular weight distribution, which comprises homopolymerizing or copolymerizing olefin. The feature of the present invention is that by using such a novel catalyst system, it is possible to produce a highly crystalline olefin polymer with a wide molecular weight distribution in good yield, which is suitable for the fields of extrusion molding and blow molding. It's at Natsutato. The titanium trichloride used in the present invention is preferably obtained, for example, by the following method. (1) Titanium tetrachloride reduced with metallic aluminum. (2) Titanium tetrachloride reduced with hydrogen. (3) Titanium tetrachloride reduced with metallic titanium. (4) Titanium tetrachloride reduced with an organoaluminum compound. (5) Titanium trichloride obtained by the methods (1) to (4) above is activated by a known method. Specific examples of activation treatment using known methods include pulverization treatment, heat treatment, and JP-A-51-16297;
JP-A-52-110793, JP-A-53-33289, JP-A-47-34478, JP-A-51-16298, JP-A-51-
No. 46598, JP-A-53-9288, JP-A-50-125986
Examples include methods described in Japanese Patent Publication No. 49-2021, Japanese Patent Application Laid-Open No. 107294-1972, and Japanese Patent Application Laid-open No. 155199-1989. However, the method is not limited to the above method. By the way, from the viewpoint of polymerization activity and stereoregularity,
Among these titanium trichlorides, especially purple α, γ,
Titanium trichloride with a δ-type layered structure is preferred. Furthermore, titanium trichloride does not need to have a pure composition of TiCl ₃ , and may be one to which an inorganic or organic aluminum compound or an electron-donating compound such as ether has been added. It may also contain reduced titanium dichloride. Next, the general formula R ¹ _3-(n+o) AlY _n X _o used in the present invention
(However, Y is selected from the group consisting of NR ² R ³ , SR ⁴ and PR ⁵ R ⁶ , and R ¹ to ^{R 6} are hydrogen and/or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an alkynyl group, a resin Represents a cyclic hydrocarbon group or an aromatic hydrocarbon group.X represents a halogen.Also, m, n
are 0.1≦m≦0.9, 0≦n≦1.9, 0.1≦m, respectively.
It is a number expressed by +n≦2. ), R ¹ to ^{R 6} are methyl, ethyl, propyl, iso-propyl, n
-butyl, iso-butyl, n-pentyl, iso-pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, vinyl, phenethyl, phenyl, benzyl, xylyl, tolyl,
Includes naphthyl and similar hydrocarbon groups, as well as compounds that are hydrogen. Among these organoaluminum compounds, those with the general formula R ¹ _3-(n+o) Al
An organoaluminum amide compound represented by (NR ² R ³ ) _n X _o is particularly preferred. The desired organoaluminum amide compound used in the present invention can be easily obtained by reacting an organoaluminium with an amine by a known method. Similarly, the general formula R ¹ _3-(n+o) Al used in the present invention
An organoaluminum thioalkoxide compound represented by (SR ⁴ ) _n X _o is obtained by reacting an organoaluminum with a thiol and sulfur. Further, an organoaluminum phosphide compound represented by the general formula R ¹ _3-(n+o) Al (PR ⁵ R ⁶ ) _n X _o can be easily obtained by reaction of organoaluminum and phosphine. The organoaluminum compound described above used in the present invention may be prepared in advance in a flask or the like and used for polymerization, or it may be directly reacted in a polymerization tank by the above-mentioned known method and then used for polymerization. You can. The molar ratio of the titanium atoms in the titanium trichloride used in the polymerization of olefin and the organoaluminum compound described above can be selected over a wide range from 10:1 to 1:500, but in particular from 1:1 to 1:100. Ranges are preferably used. Next, as the electron-donating compound used in the present invention, the following compounds can be exemplified. Examples of oxygen-containing organic compounds include ester bonds

[Formula] Ether bond (-C-O-C --), carbonate ester bond

[Formula] Compounds having a carbonyl group, a carboxyl group, an aldehyde group, an epoxy group, etc. can be mentioned. Examples of nitrogen-containing organic compounds include primary amines, secondary amines, tertiary amines, acid amides,
Examples include acid imides, cyclic nitrogen compounds, nitrile compounds, ammonium group-containing compounds, and saturated or unsaturated nitrogen compounds. Examples of the phosphorus-containing organic compound include phosphine, phosphite, phosphate, and phosphoramide. Examples of the sulfur-containing organic compound include thioether, thioketone, thioaldehyde, sulfonic acid, sulfonate, sulfate, and sulfite. Specifically, ethyl acetate, phenyl acetate, ethyl valerate, methyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate,
Ethyl anisate, di-n-butyl ether, acetone, acetylacetone, acetophenone, benzoyl chloride, acetyl chloride, triethylamine, butylamine, dibutylamine, tributylamine, pyridine, α-picoline, azobenzene, phenyl isocyanate, benzonitrile, tributylphosphine , triphenylphosphine, tributylphosphite, triphenylphosphite, tributylphosphate, triphenylphosphate, hexamethylphosphoric triamide, dibutylthioether, carbon disulfide,
Examples include butyl sulfite, dimethyl sulfone, mercaptan, trilauryl trithiophosphate, and the like. Among these electron-donating compounds, esters, phosphines, phosphites, phosphates, amines, amides, sulfites, ketones and aldehydes are particularly preferred. These electron-donating compounds may be used in the polymerization by being mixed with the organoaluminum compound in advance. By the way, regarding the effects of the electron-donating compound used in the present invention, it has the effect of improving the stereoregularity of the obtained polymer and at the same time widening the molecular weight distribution. Therefore, when an electron donating compound is not used, not only the stereoregularity of the obtained polymer is low, but also the molecular weight distribution is not widened. Therefore, the effective amount of the electron donating compound to be used is usually 0.005 to 5 mol, preferably 0.01 to 1 mol, per 1 mol of the organoaluminum compound described above.
It is a mole. Polymerization can be carried out over a temperature range of -30 to 200°C, but temperatures below 0°C result in a decrease in the polymerization rate, and temperatures above 100°C result in highly stereoregular polymers. For some reasons, it is usually preferable to carry out the reaction at a temperature in the range of 0 to 100°C. There are no particular restrictions on the polymerization pressure, but a pressure of about 3 to 100 atmospheres is desirable from the viewpoint of industrial and economical considerations. The polymerization method may be continuous or batchwise. Also, propane, butane, pentane,
Slurry polymerization using an inert hydrocarbon solvent such as hexane, heptane, or octane, liquid phase polymerization without a solvent, or gas phase polymerization is also possible. Next, olefins applicable to the present invention have 2 to 10 carbon atoms, and specific examples include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methyl-pentene-1, and 4-carbon atoms. -methyl-pentene-1, etc., but the present invention is not limited to the above compounds. The polymerization according to the present invention can be either homopolymerization or copolymerization. During copolymerization, a copolymer can be obtained by bringing two or more types of olefins into contact in a mixed state. Further, heteroblock copolymerization in which polymerization is carried out in two or more stages can also be easily carried out. According to the present invention, it is possible to obtain a polymer with high stereoregularity and a wide molecular weight distribution in high yield, particularly from α-olefin having 3 or more carbon atoms. Further, as a molecular weight control agent, for example, hydrogen can be used. Hereinafter, the method of the present invention will be explained using Examples, but the present invention is not limited to these Examples in any way. In addition, in Examples and Comparative Examples, MFI
represents melt flow index, JIS
Measured according to K6758. The melt expansion ratio (hereinafter abbreviated as SR) is calculated by measuring the diameter of a rod-shaped sample extruded during MFI measurement at 5 mm from the tip, and calculating the ratio to the diameter of the orifice of the melt flow index test device, that is, SR. = Diameter of extrudate/diameter of orifice. _W / _N is an index of molecular weight distribution, which is the ratio of weight average molecular weight _W to number average molecular weight _N , and GP
Measured using C. method (gel permeation chromatography method). The larger the value of _W / _N , the broader the molecular weight distribution. Example 1 (A) Synthesis of titanium trichloride catalyst After purging a 300 ml reaction vessel with argon, 40 ml of dry heptane and 10 ml of titanium tetrachloride were added.
This solution was kept at -5°C. Then, a solution consisting of 30 ml of dry heptane and 23.2 ml of ethylaluminum sesquichloride was added dropwise under conditions such that the temperature of the reaction system was maintained at -3 DEG C. or lower. After continuing stirring at the same temperature for 2 hours,
Heat treatment was performed at 90°C for 2 hours. After separation and washing, 16 g of a titanium trichloride composition was obtained. Next, 11.0 g of the above titanium trichloride composition was slurried in 55.0 ml of toluene to form a TiCl ₃ composition/I ₂ /
Iodine and di-n-butyl ether were added so that the molar ratio of di-n-butyl ether was 1/0.1/1.0, and the reaction was carried out at 95° C. for 1 hour.
After the reaction, the product was separated, washed, and dried under reduced pressure to obtain 7.5 g of titanium trichloride catalyst. (B) Synthesis of organoaluminum amide After purging a 200 ml flask with argon, 30 ml of dry heptane and 3.0 g of diethylaluminum hydride were collected, and 2.6 g of diethylamine was gradually added dropwise at room temperature while stirring. After the dropwise addition was completed, the temperature was raised to 50°C and stirred at this temperature for 30 minutes. Then, diethyl aluminum chloride
Add a solution of 12.6g diluted in 100ml of heptane,
Further stir at 50°C for 30 minutes to obtain Et _2.0 Al (NEt ₂ ) _0.25
An organoaluminum amide with a composition of Cl _0.75 was synthesized. (C) Polymerization of propylene () A stirred stainless steel autoclave with an internal volume of 5 was replaced with argon and dried heptane 1.5
, Et _2.0 Al(NEt ₂ ) _0.25 Cl _0.75 prepared in (B) above
15.0 mmol, 2.25 mmol of p-ethyl anisate, and the titanium trichloride catalyst synthesized in (A) above.
120 mg was charged, and hydrogen corresponding to a partial pressure of 0.26 Kg/cm ² was added. Next, the temperature of the autoclave was raised to 60°C, and then propylene was introduced under pressure to 6 kg/cm ² to start polymerization, and the polymerization was continued for 2 hours while replenishing propylene to maintain this pressure. After the polymerization was completed, the introduction of monomers was stopped, unreacted monomers were purged, and 100 ml of butanol was added to decompose the catalyst. The produced polymer was filtered through a Buchner filter, washed three times with 500 ml of heptane, and dried at 60°C, yielding 144 g of polypropylene. The heptane is removed from the liquid by steam distillation,
3.6 g of amorphous polymer was obtained. The heptane insoluble part (hereinafter abbreviated as HIP) in the total polymer yield is 97.7%, and the boiling heptane insoluble part (hereinafter abbreviated as II) in the HIP part is 98.1%.
It was hot. Also, g TiCl ₃ solid catalyst, Rp expressed as polymer yield per hour (g polypropylene/
gTiCl ₃ hr) was 615. In addition, MFI of the obtained polypropylene powder
is 2.2, SR is 1.49, _W / _N value is 14.4,
Polypropylene with a wide molecular weight distribution was obtained. (D) Polymerization of propylene () A stirred stainless steel autoclave with an internal volume of 5 was replaced with argon and prepared as in (B) above.
Et _2.0 Al (NEt ₂ ) _0.25 Cl _0.75 15.0 mmol, p-ethyl anisate 3.0 mmol, and 65 mg of the titanium trichloride catalyst synthesized in (A) above were charged, and 0.66 Kg/cm ²
Hydrogen corresponding to a partial pressure of was added. Then, 1.4 kg of liquid propylene was pressurized into the autoclave, and the autoclave was kept at 60°C to continue polymerization for 2 hours. After the polymerization was completed, unreacted monomers were purged, and 100 ml of methanol was added to decompose the catalyst. The produced polypropylene was filtered using a Buchner filter and dried under reduced pressure at 60°C to obtain 224 g of polypropylene. The polymerization activity was 1720 in terms of Rp. In addition, the boiling heptane insoluble portion was 96.6%. Also, the MFI of the obtained polypropylene powder is 0.85, and the SR is 1.50.
_{The W} / _N value was 15.1, and polypropylene with a wide molecular weight distribution was obtained. Comparative Example 1 The same procedure as in Example 1 was used, except that 145 mg of TiCl ₃ AA (manufactured by Toho Titanium Co., Ltd.), which is usually used industrially, and 15.0 mmol of diethylaluminium chloride were used, and ethyl p-anisate was not used. Polymerization of propylene was carried out in the same manner as in (C). Rp=240, HIP%=92.2, II%=96.3.
In addition, the MFI of the obtained polypropylene powder is 1.5,
The SR was 1.36 and _{the W} / _N value was 6.5. The molecular weight distribution of the polypropylene obtained compared to Example 1 is narrow. Comparative Example 2 Propylene was prepared in the same manner as in Example 1 (D) except that 92 mg of TiCl ₃ AA (manufactured by Toho Titanium Co., Ltd.) and 15.0 mmol of diethylaluminium chloride were used, and ethyl p-anisate was not used. Polymerization was carried out. Rp=494, and the boiling heptane insoluble portion was 92.4%. The MFI of the obtained polypropylene powder is 2.2,
The SR was 1.38 and _{the W} / _N value was 6.7. Comparative Example 3 Titanium trichloride catalyst 104 synthesized in (A) of Example 1
Example 1 except that 15.0 mmol of diethylaluminium chloride was used instead of 0.2 mg and Et _0.2 Al(NEt ₂ ) _0.25 Cl _0.75 , and ethyl p-anisate was not used.
Polymerization of propylene was carried out in the same manner as in (C). Rp=816, HIP%=97.4, II%=98.6. In addition, the MFI of the obtained polypropylene powder is
1.7, SR was 1.37, and _W / _N value was 6.5. It can be seen that the molecular weight distribution of the polypropylene obtained in comparison with Example 1 is narrow. Comparative Example 4 In Comparative Example 3, propylene was polymerized in the same manner as in Comparative Example 3, except that 2.25 mmol of p-ethyl anisate was used. Rp=771, HIP%=
97.7, II% = 98.9. Also, the MFI of the obtained polypropylene powder is 1.0, SR is 1.35, _W / _N
The value was 6.6. Compared to Comparative Example 3, it can be seen that by using p-ethyl anisate in this case, although the stereoregularity is slightly improved, the molecular weight distribution is almost unchanged. Comparative Example 5 Titanium trichloride catalyst 133 synthesized in (A) of Example 1
Example 1 except that 15.0 mmol of triethylaluminum and 3.75 mmol of ethyl p-anisate were used in place of Et _2.0 Al(NEt ₂ ) _0.25 Cl _0.75 .
Polymerization of propylene was carried out in the same manner as in (C). Rp=557, HIP% 89.1, II%=94.9. In addition, the MFI of the obtained polypropylene powder is 2.3,
The SR was 1.40 and _{the W} / _N value was 7.4. It can be seen that the molecular weight distribution is narrower than in Example 1. Comparative Example 6 Polymerization of propylene was carried out in the same manner as in Example 1 (C) except that p-ethyl anisate was not used. Rp=2640, HIP%=74.1, II%=84.5. Also, MFI is 9.4, SR is 1.42, and _W / _N value is
It was 6.4. Compared to Example 1, it can be seen that without the use of p-ethyl anisate, the stereoregularity is significantly reduced and the molecular weight distribution is not broadened. Examples 2 to 7 In the polymerization method (C) of Example 1, propylene was polymerized using various electron-donating compounds shown in Table 1 instead of ethyl p-anisate. The results are shown in Table 1.

[Table] Examples 8 to 17 Organoaluminum amide compounds having various compositions were synthesized by reacting organoaluminum and amine according to the method for synthesizing organoaluminum amide in Example 1 (B). Furthermore, by reacting triethylaluminum with sulfur and diphenylphosphine, diethylaluminum thioethoxide and diethylaluminium diphenylphosphine were synthesized, and by further mixing each with diethylaluminum chloride, the products shown in Table 2 were synthesized. Organoaluminum thioalkoxides and organoaluminium phosphides of the following compositions were synthesized. The titanium trichloride catalyst synthesized in Example 1 (A)
Propylene was prepared in the same manner as in (C) of Example 1, except that 15 mmol of organoaluminum compounds of the various compositions described above were used as cocatalysts and 2.25 mmol of ethyl p-anisate was used as an electron donor. Polymerization was carried out. The results are shown in Table 2.
Good results were obtained in all cases.

【table】

[Table] Example 18 (C) of Example 1 except that 170 mg of TiCl ₃ AA (manufactured by Toho Titanium Co., Ltd.) was used as a titanium trichloride catalyst.
Polymerization of propylene was carried out in a similar manner. Rp=304, HIP%=93.5, II%=96.2.
In addition, the MFI of the obtained polypropylene powder was 2.1,
The SR was 1.50 and _{the W} / _N value was 14.1. It can be seen that a polymer with a wide molecular weight distribution was obtained. Example 19 (A) Synthesis of organoaluminium-reduced titanium trichloride
After purging the 300 ml flask with argon, 80 ml of dry heptane and 20 ml of titanium tetrachloride were added, and the solution was kept at -5°C. Then, a solution consisting of 60 ml of dry heptane and 23.2 ml of diethylaluminum chloride was added dropwise to the reaction system so as to maintain the temperature at -3°C. After the addition is complete, continue stirring for an additional 30 minutes, then
The temperature was raised to 70°C, and stirring was continued for an additional hour. After the reaction, the reduced product was allowed to stand still and separated into solid and liquid, washed with 100 ml of heptane, and dried under reduced pressure.
29.6 g of organoaluminium-reduced titanium trichloride was obtained. (B) Heat treatment of organoaluminium-reduced titanium trichloride 10 g of organoaluminium-reduced titanium trichloride synthesized in (A) above was slurried in n-decane, and heat-treated at 140° C. for 2 hours at a slurry concentration of 0.2 g/cc. After the reaction, the supernatant was extracted and washed twice with 50 ml of heptane to obtain a heat-treated titanium trichloride solid. (C) Polymerization of propylene Propylene was polymerized under the same conditions as in (C) of Example 1, except that the heat-treated titanium trichloride solid synthesized in (B) above was used. Rp=311, HIP%=93.3, II%=96.5. Also, the MFI of the obtained polypropylene powder
was 1.9, SR was 1.48, and _W / _N was 13.6. Example 20 (A) Synthesis of titanium trichloride catalyst 10.6 g of organoaluminium-reduced titanium trichloride synthesized in (A) of Example 22 was suspended in 50 ml of dry heptane, and then
Adding 1.2 molar ratio of diisoamyl ether,
The mixture was stirred at 40°C for 1 hour. After the reaction is complete, remove the supernatant and add another 50 ml.
After washing with heptane three times and drying, a titanium trichloride ether-treated solid was obtained. Next, the above titanium trichloride ether treated solid 5
g was added to a solution consisting of 15 ml of heptane and 10 ml of titanium tetrachloride, and the mixture was reacted at 70°C for 2 hours. After the reaction, the supernatant was extracted, washed three times with 50 ml of heptane, and dried to prepare a titanium trichloride catalyst. (B) Polymerization of propylene Propylene was polymerized in the same manner as in (C) of Example 1, except that the titanium trichloride catalyst synthesized in (A) above was used. Rp=640, HIP%=97.5, II%=98.2. In addition, the obtained polypropylene powder
MFI is 2.0, SR is 1.49, _W / _N value is 14.5,
It can be seen that a polymer with a wide molecular weight distribution was obtained. Example 21 (A) Synthesis of titanium trichloride catalyst After purging a 300 ml flask with argon, 80 ml of dry toluene, 8.6 ml of diethylaluminum chloride, and 23 ml of di-n-butyl ether were added.
was added and the solution was kept at 10°C. Next, 20 ml of dry toluene, 15 titanium tetrachloride
ml of the solution was added dropwise so that the temperature of the reaction system was maintained at 10°C. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then heated and precipitated at 50°C for 30 minutes and at 100°C for 1 hour. After the reaction was completed, the supernatant was extracted, washed twice with 100 ml of toluene and twice with 100 ml of heptane, and then dried under reduced pressure to give 19.4
A titanium trichloride catalyst of g was synthesized. (B) Polymerization of propylene Propylene was polymerized in the same manner as in (C) of Example 1, except that the titanium trichloride catalyst synthesized in (A) above was used. Rp=622, HIP%=97.6, II%=98.1. Also, the MFI of the obtained polypropylene powder
was 3.1, SR was 1.52, and _W / _N was 14.0. It can be seen that a polymer with a wide molecular weight distribution was obtained in this case as well. Example 22 Titanium trichloride catalyst 110 obtained in Example 1 (A)
Copolymerization of ethylene and propylene was carried out using mg. That is, in the polymerization of propylene in (C) of Example 1, polymerization was carried out in the same manner as in (C) of Example 1, except that a mixed gas of ethylene and propylene containing 2.5 vol% ethylene was used. is Rp=709
It was hot. Moreover, HIP% was 96.0%. In addition, the MFI of the obtained copolymer was 3.4, and the SR was
1.52, _{the W} / _N value was 11.4, and a copolymer with a wide molecular weight distribution was obtained. When the ethylene content of the copolymer was analyzed by infrared absorption spectrum, it was found to be 1.8 wt%.

[Brief explanation of the drawing]

FIG. 1 is a flowchart to aid understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited thereto.

Claims (1)

[Claims] 1 (A) Titanium trichloride, (B) General formula R ¹ _3-(n+o) AlYmXn (where Y is
selected from the group consisting of NR ² R ³ , SR ⁴ and PR ⁵ R ⁶ , R ¹ to ^{R 6} are hydrogen and/or carbon number is 1
~18 alkyl group, alkenyl group, alkynyl group, alicyclic hydrocarbon group, or aromatic hydrocarbon group. X represents halogen. Also, m and n are 0.1≦m≦0.9 and 0≦, respectively.
It is a number expressed by n≦1.9, 0.1≦m+n≦2. ) an organoaluminum compound represented by
and (C) using a catalyst system consisting of an electron-donating compound to
A method for producing a highly crystalline olefin polymer with a wide molecular weight distribution, characterized by homopolymerizing or copolymerizing olefin.