JPH0349921B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a solid catalyst component for olefin polymerization. Generally, as a method for producing olefin polymers, it is well known to use a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound of group - of the periodic table and a metal or organometallic compound of group I of the periodic table. Titanium trichloride compositions are particularly used in the industrial production of olefin polymers such as propylene and butene-1. However, in this production method, an amorphous polymer is produced as a by-product in addition to a highly regular olefin polymer which has high industrial utility value. This amorphous polymer has little industrial utility value;
This has a large negative effect on the mechanical properties when the olefin polymer is processed into film fibers and other processed products. Furthermore, the formation of the amorphous polymer causes a loss of raw material monomers, and at the same time, production equipment necessary for removing the amorphous polymer is required, resulting in an extremely large disadvantage from an industrial perspective. Therefore, it can be a great advantage if such amorphous polymers are not produced at all, or if they are produced at all, but only to a very small extent. On the other hand, catalyst residue remains in the olefin polymer obtained by this polymerization method, and this catalyst residue causes various problems such as stability and processability of the olefin polymer, and it is difficult to remove and stabilize the catalyst residue. Equipment for this purpose is required. This drawback can be improved if the catalytic activity expressed as the weight of the olefin polymer produced per unit weight is increased, and equipment for removing the catalyst residue is no longer required, which reduces the production cost required for producing the olefin polymer. It is also possible to lower the The methods for producing titanium trichloride include (1) reducing titanium tetrachloride with hydrogen and then pulverizing it with a ball mill to activate it; (2) reducing it with metallic aluminum and then pulverizing it with a ball mill to activate it. (3) A reduced solid obtained by reduction with an organoaluminum compound at a temperature of -30 to 30°C is heat-treated at a temperature of 120 to 180°C. However, the above titanium trichloride has catalytic activity,
Stereoregularity is not fully satisfactory in any respect. In addition, a method in which the reduced solid produced by reducing titanium tetrachloride with an organoaluminum compound is treated with a complexing agent and further reacted with titanium tetrachloride (Japanese Patent Publication No. 53-3356), and titanium tetrachloride treatment method (Special Publication No. 54-3480),
A method of reducing an alkoxy group-containing titanium compound with an organoaluminium compound in the presence of an ether compound, adding titanium tetrachloride and an ether compound to form a titanium liquid, and heating this to redeposit the titanium compound No. 56-18608, JP-A-Sho
56-20002) etc. have been proposed. As a result of intensive studies on titanium compounds containing hydrocarbyloxy groups, the present inventors found that
Contains a hydrocarbyloxy group obtained by treating a solid product obtained by reducing a titanium compound represented by the general formula Ti(OR ¹ ) _o X _4-o with an organoaluminum compound with an ether compound and titanium tetrachloride. When olefin polymerization was carried out using a solid catalyst component with an aluminum compound, the inventors discovered that the catalyst activity was high and the stereoregularity of the resulting polymer was high, leading to the present invention. That is, the present invention is based on the general formula Ti(OR ¹ ) _o X _4-o (R ¹
represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number satisfying 0<n≦4. ) is a titanium compound represented by the general formula A1R ² _n Y _3-n (R ² is a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen atom, m
represents a number of 1<m≦3. ) A solid product containing a hydrocarbyloxy group that is insoluble in a hydrocarbon solvent obtained by reduction with an organoaluminum compound represented by the formula is slurried in the presence of an ether compound and titanium tetrachloride at a temperature of 30°C to 120°C. The present invention relates to a method for producing a solid catalyst component for olefin polymerization, which is characterized in that the solid component is treated in a state where the solid component is treated as a catalyst. The present invention is characterized by high catalytic activity and a large amount of polymer produced per solid catalyst component and per titanium, thereby enabling a non-deashing process that does not require a step for removing catalyst residue. Furthermore, since the produced polymer has high stereoregularity, a step of extracting and removing an amorphous polymer is not necessary. In addition, as described in Japanese Patent Publication No. 53-3356, titanium tetrachloride is reduced with an organoaluminum compound and then subjected to various activation treatments to synthesize a highly active titanium trichloride catalyst. Since the reaction is usually carried out at a low temperature of 0° C. or lower, expensive refrigeration equipment is required. However, in the present invention, the reduction reaction temperature when reducing the titanium compound represented by the general formula Ti(OR ¹ ) _o X _4-o with an organoaluminum compound is usually 10°C to 80°C.
temperature range, and has the advantage of not requiring expensive refrigeration equipment as mentioned above. The general formula used in the present invention is Ti(OR ¹ ) _o X _4-o (R ¹
represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number satisfying 0<n≦4. ) As a specific example of R ¹ in the titanium compound represented by
Methyl, ethyl, n-propyl, iso-propyl,
Alkyl groups such as n-butyl, iso-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, phenyl, cresyl, xylyl, naphthyl, etc. Examples include an allyl group, a cycloalkyl group such as cyclohexyl and cyclopentyl, an aryl group such as propenyl, and an aralkyl group such as benzyl. Particularly preferred are linear alkyl groups having 2 to 18 carbon atoms and allyl groups having 6 to 18 carbon atoms. It is also possible to use titanium compounds having two or more different OR ¹ groups. The halogen atom represented by X includes chlorine,
Examples include bromine and iodine. In particular, chlorine gives favorable results. A known method can be used to synthesize the titanium compound represented by the general formula Ti(OR ¹ ) _o x _4-o (0<n≦4). For example, a method in which Ti(OR ¹ ) ₄ and TiX ₄ are reacted at a predetermined ratio, or a method in which TiX ₄ and a corresponding alcohol are reacted in a predetermined amount can be used. The value of n in the titanium compound represented by the general formula Ti(OR ¹ ) _o x _4-o is 0<n≦4, especially 1≦n≦4.
is preferred. Next, the general formula A1R ² _n Y _3-n used in the reduction reaction
(R ² is a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen atom, and m is a number of 1≦m≦3). Specific examples of organoaluminum compounds include:
Methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, ethylaluminum sesquichloride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, trimethylaluminum, triethylaluminum, triisobutylaluminum, ethyldicyclohexylaluminum, trifium Examples include enylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum bromide, and diethylaluminum iodide. Among these, diethylaluminum chloride and ethylaluminum sesquichloride give particularly preferable results. Reduction reactions include pentane, hexane, heptane,
Preferably, the titanium compound and organoaluminum compound are diluted to a concentration of 10 to 70% by weight with an inert hydrocarbon solvent such as octane, decane, toluene, or decalin. Reduction reaction temperature is 10~80℃, preferably 25~70℃
It is. The reduction reaction time is not particularly limited, but 1 to 6 hours is usually suitable. The molar ratio of the titanium compound and the organoaluminum compound can be freely changed depending on the purpose. Favorable results are obtained with 0.5 diethylaluminum chloride per mole of titanium compound.
~1.5 mol, in the case of ethylaluminum sesquichloride 1.5-2.5 mol. After completion of the reduction reaction, a post-reaction may be further carried out at a temperature of 30 to 100°C. The solid product containing a hydrocarbyloxy group that is insoluble in a hydrocarbon solvent obtained by the reduction reaction is separated into solid and liquid, and then separated into an inert hydrocarbon solvent such as pentane, hexane, heptane, octane, decane, toluene, xylene, decalin, etc. After washing several times with
React with an ether compound and titanium tetrachloride. Ether compounds include diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-amyl ether, diisoamyl ether, dineopentyl ether, di-n-hexyl ether, di-n-
octyl ether methyl-n-butyl ether,
Dialkyl ethers such as methyl-isoamyl ether and ethyl-isobutyl ether are preferred. Particularly preferred are di-n-butyl ether and diisoamyl ether. The amount of the ether compound used is 0.1 to 5 mol, particularly preferably 0.3 to 3 mol, per mol of titanium atom contained in the solid product containing a hydrocarbyloxy group. The amount of titanium tetrachloride added is 0.1 to 10 moles, particularly preferably 0.5 to 5 moles, per mole of titanium atoms contained in the solid product. The amount of titanium tetrachloride used per mole of the ether compound is 0.5 to 10 moles, particularly preferably 1.5 to 5 moles. The reaction of the solid product containing hydrocarbyloxy groups insoluble in hydrocarbon solvents with the ether compound and titanium tetrachloride is carried out in a slurry state. Solvents used to slurry the solid product containing hydrocarbyloxy groups include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, aromatic hydrocarbons such as toluene, xylene, decalin, etc. Examples include alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aliphatic hydrocarbons are particularly preferred. Slurry concentration is 0.05-0.5g solids/cc solvent, especially
0.1-0.3 g solid/cc solvent is preferred. The reaction temperature is preferably 30 to 120°C, particularly 45 to 100°C. There is no particular limit to the reaction time, but it is usually 30 minutes to 6 minutes.
Time is favorable. The methods for adding the solid product, ether compound and titanium tetrachloride include adding the ether compound and titanium tetrachloride to the solid product, and conversely adding the solid product to a solution of the ether compound and titanium tetrachloride. Either method may be used. In the method of adding the ether compound and titanium tetrachloride to the solid product, a method of adding the ether compound and then adding titanium tetrachloride, or a method of adding the ether compound and titanium tetrachloride at the same time is particularly preferred. In the solid catalyst component obtained in the present invention, the hydrocarbyloxy group is present per mole of titanium atom,
0.0001-0.3 mol, particularly preferably 0.0002-0.15
Contains moles. If the amount of hydrocarbyloxy groups is greater than this range, the catalytic activity will be lowered, and the stereoregularity of the resulting polymer will also be lowered during the polymerization of α-olefin. Conversely, when the amount of hydrocarbyloxy groups is less than this range, the catalytic activity is particularly reduced. The solid catalyst component obtained in the above reaction is separated into solid and liquid, washed several times with an inert hydrocarbon solvent such as hexane or heptane, and then used for polymerization. Next, the organoaluminum compounds used in the polymerization of olefin in the present invention include trialkylaluminum, dialkylaluminum hydride,
Dialkyl aluminum chlorides, dialkyl aluminum alkoxides, dialkyl aluminum siloxides and mixtures thereof are used. Specific examples include dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide,
Trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diethylaluminium ethoxide and mixtures thereof are preferably used. The amount of the organoaluminum compound to be used can be selected from a wide range of 0.1 to 500 mol per mol of titanium atom in the hydrocarbyloxy group-containing solid catalyst component, but is preferably in the range of 0.5 to 200 mol. Polymerization can be carried out at temperatures ranging from 0°C to 300°C. However, in the highly stereoregular polymerization of α-olefins such as propylene,
For reasons such as the inability to obtain a polymer having a high degree of stereoregularity, it is generally preferable to carry out the reaction at a temperature in the range of 0°C to 100°C. There are no particular limitations on the polymerization pressure, but a pressure of about 3 to 2000 atm is desirable from the viewpoint of industrial and economical considerations. The polymerization method can be either continuous or batchwise. Next, α-olefins to which the present invention can be applied are those having 2 to 10 carbon atoms, and specific examples include ethylene, propylene, butene-1, pentene-1, and
-Methylpentene-1, hexene-1, etc., but the present invention should not be 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 contacting two or more types of α-olefins in a mixed state. Heteroblock copolymerization, in which polymerization is carried out in two or more stages, can also be carried out easily. Polymerization methods include butane, pentane, hexane,
Slurry polymerization using an inert hydrocarbon solvent such as heptane or octane, solution polymerization in which the resulting polymer is polymerized while being dissolved in the inert hydrocarbon solvent, bulk polymerization in a liquefied monomer without a solvent,
Gas phase polymerization in gaseous monomers is possible. It is also possible to add chain transfer agents such as hydrogen to adjust the molecular weight of the polymer. It is also possible to add an electron-donating compound to the polymerization system for the purpose of improving the stereoregularity of the polymer. The method of the present invention will be explained below using Examples, but the present invention is not limited to these Examples in any way. Example 1 (A) Synthesis of solid product After purging a flask with an internal volume of 500 ml equipped with a stirrer and a dropping funnel with argon, tetraO
- 100 g of cresoxy titanium and 250 ml of toluene were put into a flask, and the tetra-O-cresoxy titanium was dissolved. Next, a solution consisting of 100 ml of toluene and 47.8 ml of ethylaluminum sesquichloride was gradually added dropwise from the dropping funnel over 2 hours while maintaining the temperature inside the flask at 60°C. After the dropwise addition was completed, the mixture was further stirred at 60°C for 1 hour, and then allowed to stand at room temperature for solid-liquid separation.
After repeating washing four times with 200 ml, drying under reduced pressure gave a brown solid product. In 1 g of this solid product, 3.8 mmol of titanium,
It contained 4.7 mmol of O-cresoxy groups. In addition, the X
No characteristic peak of titanium trichloride crystal was observed in the line diffraction diagram. (B) Synthesis of solid catalyst component After purging a flask with an internal volume of 100 ml with argon, 5.8 g of the solid product prepared in (A) above and n
- 29 ml of heptane was charged into the flask, and the temperature inside the flask was maintained at 65°C. Next, 4.4 ml of di-n-butyl ether and 5.7 ml of titanium tetrachloride were added, and the reaction was carried out at 65°C for 1 hour. After standing at room temperature and separating solid and liquid, the mixture was washed four times with 50 ml of n-heptane and dried under reduced pressure to obtain a purple solid catalyst component. 1 g of this solid catalyst component contained 4.8 mmol of titanium and 0.44 mmol of O-cresoxy groups. (C) Polymerization of propylene After purging a stainless steel autoclave with an internal volume of 130 ml and stirring with a magnetic stirrer with argon, 250 mg of diethyl aluminum chloride and 27.7 g of the solid catalyst component obtained in (B) above were added.
mg, and 80 ml of liquefied propylene were charged into an autoclave. The autoclave was kept at 60°C for 1 hour with stirring. After releasing the excess propylene, the resulting polypropylene was air-dried overnight.
36.0 g of polypropylene was obtained. Therefore, the yield (g) of polypropylene per 1 g of solid catalyst component (hereinafter abbreviated as PP/cat) is
PP/cat=1300. In addition, the obtained polypropylene powder was boiled
- The percentage of the residue extracted with heptane for 6 hours (hereinafter abbreviated as 1Y (%)) was 1Y = 96.8%. Comparative Example 1 (A) Synthesis of solid catalyst component After purging a 200 ml flask equipped with a stirrer and a dropping funnel with argon, 38 ml of n-heptane and 10 ml of titanium tetrachloride were put into the flask, and the temperature inside the flask was lowered. was kept at 50℃. Next, 20.7 ml of ethylaluminum sesquichloride and n-
A solution consisting of 50 ml of heptane was gradually added dropwise from the dropping funnel over 90 minutes while maintaining the temperature inside the flask at 50°C. After dropping, the temperature was raised to 60℃,
Stirred for 1 hour. Leave to stand at room temperature for solid-liquid separation, and remove 50% of n-heptane.
After washing was repeated 5 times with ml, a solid product was obtained by drying under reduced pressure. After purging a flask with an internal volume of 100 ml with argon, 7.3 g of the above solid product and 36.5 g of n-heptane were added.
Pour ml into the flask and bring the temperature inside the flask to 65.
It was kept at ℃. Next, 8.0 ml of di-n-butyl ether and 10.4 ml of titanium tetrachloride were added, and the reaction was carried out at 65°C for 1 hour. After standing at room temperature and separating solid and liquid, the mixture was washed four times with 50 ml of n-heptane and dried under reduced pressure to obtain a solid catalyst component. The solid catalyst component contained 5.46 mmol of titanium. (B) Polymerization of propylene Using the solid catalyst component synthesized in (A) above, propylene was polymerized in the same manner as in (C) of Example 1. PP/cat = 200, IY = 79.7% It was hot. Example 2 In the synthesis of the solid catalyst component (B) of Example 1,
A solid catalyst component was synthesized under the same conditions as in Example 1 except that the amount of titanium tetrachloride used was changed to 8.6 ml.
1 g of this solid catalyst component contains 5.7 mmol of titanium.
It contained 0.34 mmol of O-cresoxy groups. When propylene was polymerized in the same manner as in Example 1 (C), PP/cat=1080, IY=98.4
It was %. Example 3 In the synthesis of the solid catalyst component (B) of Example 1,
A solid catalyst component was synthesized under the same conditions as in Example 1 except that the reaction temperature was changed to 75°C. 1 g of this solid catalyst component contained 5.8 mmol of titanium and 0.19 mmol of O-cresoxy groups. (C) of Example 1
When propylene was polymerized in the same manner as above, PP/cat = 1150 and IY = 98.5%. Example 4 After purging a flask with an internal volume of 100 ml with argon, 6.3 g of the solid product synthesized in (A) of Example 1 and n
- Pour 32 ml of heptane and bring the temperature inside the flask to 30
It was kept at ℃. Then di-iso-amyl ether 5.7
ml and treated at 35°C for 1 hour, then 6.2ml of titanium tetrachloride was added, the temperature was raised to 65°C, and the reaction was carried out at 65°C for 1 hour. After standing at room temperature and separating solid and liquid, the mixture was washed five times with 50 ml of n-heptane and dried under reduced pressure to obtain a solid catalyst component. 1 g of this solid catalyst component contains 5.3 mmol of titanium.
It contained 0.19 mmol of O-cresoxy groups. When propylene was polymerized in the same manner as in Example 1 (C), PP/cat = 1130, IY = 97.6%.
It was hot. Example 5 (A) Synthesis of solid product A flask with an internal volume of 300 ml equipped with a stirrer and a dropping funnel was purged with argon, and then replaced with toluene.
Pour 15ml and 15ml of titanium tetrachloride into the flask,
The temperature inside the flask was maintained at 80°C. Next, 40ml of toluene and 28.7ml of O-cresol.
The solution was gradually added dropwise from the dropping funnel over 1 hour while maintaining the temperature inside the flask at 80°C. After the dropwise addition was completed, the mixture was further stirred at 80°C for 1.5 hours. After cooling the temperature inside the flask to 50℃, n-
40ml heptane and diethylaluminum chloride
While maintaining the temperature inside the flask at 50° C., 17 ml of the solution was gradually added dropwise from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the temperature was raised to 60°C and stirred for 1 hour. The mixture was allowed to stand at room temperature for solid-liquid separation, washed six times with 100 ml of n-heptane, and then dried under reduced pressure to obtain a brown solid product. In 1 g of this solid product, 4.4 mmol of titanium,
It contained 3.6 mmol of O-cresoxy groups. In addition, the X
No characteristic peak of titanium trichloride crystal was observed in the line diffraction diagram. (B) Synthesis of solid catalyst component A solid catalyst component was synthesized under the same conditions as in the synthesis of the solid catalyst component in (B) of Example 1, except that 5.8 g of the solid product synthesized in (A) above was used. 1 g of this solid catalyst component contained 4.7 mmol of titanium and 0.21 mmol of O-cresoxy groups. (C) Polymerization of propylene Propylene was polymerized in the same manner as in (C) of Example 1 using the solid catalyst component synthesized in (B) above. PP/cat=1160, IY=97.1%. Example 6 (A) Synthesis of solid product A 500 ml flask equipped with a stirrer and a dropping funnel was purged with argon, and then 110 ml of n-heptane and 67 ml of tetra-n-butoxytitanium were added.
into the flask, and the temperature inside the flask was raised to 35℃.
I kept it. A solution consisting of 108 ml of n-heptane and 44.8 ml of ethylaluminum sesquichloride was gradually added dropwise from the dropping funnel over 2 hours while maintaining the temperature inside the flask at 35°C. After dripping
The temperature was raised to 60°C and stirred for 1 hour. The mixture was allowed to stand at room temperature for solid-liquid separation, washed four times with 100 ml of n-heptane, and then dried under reduced pressure to obtain a reddish-brown solid product. In 1 g of this solid product, 5.2 mmol of titanium,
It contained 7.0 mmol of n-butoxy groups. (B) Synthesis of solid catalyst component After purging a flask with an internal volume of 100 ml with argon, 5.4 g of the solid product prepared in (A) above and n
- 27ml of heptane was charged into the flask, and the temperature inside the flask was maintained at 65°C. Next, 4.8 ml of di-n-butyl ether and 15.6 ml of titanium tetrachloride were added, and the reaction was carried out at 65°C for 1 hour. After standing at room temperature and separating solid and liquid, the mixture was washed four times with 50 ml of n-heptane and dried under reduced pressure to obtain a solid catalyst component. 1 g of this solid catalyst component contained 5.4 mmol of titanium and 0.4 mmol of n-butoxy groups. (C) Polymerization of propylene Using the solid catalyst component obtained in (B) above, Example 1
When propylene was polymerized in the same manner as in (C), PP/cat was 730 and IY was 98.5%. Examples 7 to 9 Example 5 except that in the synthesis of the solid product of Example 5, various alcohols and phenols as shown in Table 1 were used instead of O-cresol.
The solid product was synthesized in a similar manner. Using these solid products, a solid catalyst component was synthesized in the same manner as in Example 1 (B) except that the reaction temperature was changed to 75°C. Using these solid catalyst components, propylene was polymerized in the same manner as in Example 1 (C). The results are shown in Table 1.

[Table] Example 10 Using the solid catalyst component prepared in Example 6, ethylene and butene-1 were copolymerized. After purging a stainless steel autoclave with an internal volume of 130 ml and stirring with a magnetic stirrer with argon, 70 ml of isoparaffinic hydrocarbon solvent (trade name IP Solvent 2028, Idemitsu Petrochemical KK) and 32.5 mg of triethyl aluminum were added at a temperature of 190°C. Placed in an autoclave. Next, a mixed gas of ethylene and butene-1 (butene-1 concentration
25% by weight) was supplied to the autoclave and dissolved in the solvent, and then 15.7 mg of the solid catalyst component was added. A mixed gas was supplied so that the total pressure was 6 Kg/cm ² , and polymerization was carried out at 190° C. for 1 hour. After the polymerization was completed and unreacted monomers were purged, 1 ml of n-decyl alcohol was added. The obtained polymer was poured into a large amount of methanol, separated into solid and liquid, and then dried under reduced pressure at 70°C for 6 hours. 2.51 g of ethylene, butene-1 copolymer was obtained. Therefore, ethylene per gram of solid catalyst component,
Yield (g) of butene-1 copolymer (hereinafter referred to as PE/cat
) was PE/cat = 160. In addition, from the measurement of infrared absorption spectrum, it was found that there are 21.3 ethyl groups per 1000 carbon atoms in this copolymer.
The content of 1 was 8.5% by weight. Comparative Example 2 Using the solid catalyst component prepared in Comparative Example 1, copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 10. The catalyst activity was PE/cat=24. Further, the content of butene-1 in the copolymer was 4.8% by weight. Example 11 Using the solid catalyst component prepared in Example 5, copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 10. The catalytic activity was PE/cat=146. The content of butene-1 in the copolymer was 8.1% by weight. Example 12 Propylene-ethylene block copolymerization A stirred stainless steel autoclave with an internal volume of 5 was purged with argon, and 45.9 mg of the solid catalyst component prepared in Example 4 and 3.0 g of diethylaluminium chloride were charged at a rate of 0.79 Kg/ ^cm2. Hydrogen corresponding to the pressure was added. Then, 1.3 kg of liquefied propylene was pressurized into the autoclave, and the autoclave was kept at 60°C to continue polymerization for 1 hour. Next, after purging unreacted monomers, the autoclave was replaced with argon. 0.15 again at 60℃
After adding hydrogen equivalent to a partial pressure of Kg/cm ² , feed propylene gas until the total pressure reaches 8.0 Kg/cm ² G, then feed ethylene gas until the total pressure reaches 10 Kg/cm ² G. I fed it. Thereafter, a mixed gas of ethylene/propylene = 50/50 Vol% was fed so as to maintain the total pressure at 10 Kg/cm ² G, and ethylene/propylene copolymerization was carried out in the gas phase for 2.3 hours. After the polymerization was completed, unreacted monomers were purged to obtain 183 g of a propylene-ethylene block copolymer with good powder properties. The propylene-ethylene block copolymer contained 43% by weight of propylene homopolymer and 57% by weight of propylene-ethylene copolymer.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1 General formula Ti(OR ¹ ) _o X _4-o (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and n is 0<n≦4
represents the number of ), the titanium compound represented by
Reduced with an organoaluminium compound represented by the general formula A1R ² _n Y _3-n (R ² is a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen atom, and m is a number in the range 1≦m≦3). Afterwards, after solid-liquid separation, the solid product containing a hydrocarbyloxy group that is insoluble in the hydrocarbon solvent obtained by washing with an inert hydrocarbon solvent is heated at 30°C in the presence of an ether compound and titanium tetrachloride.
A method for producing a solid catalyst component for olefin polymerization, which comprises processing in a slurry state at a temperature of 120°C. 2. Claim 1, in which n of the titanium compound represented by the general formula Ti(OR ¹ ) _o X _4-o satisfies 1≦n≦4.
A method for producing a solid catalyst component for olefin polymerization as described in 2. 3. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein X in the titanium compound represented by the general formula Ti(OR ¹ ) _o X _4-o is chlorine. 4. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the hydrocarbon group R ¹ is a linear alkyl group having 2 to 18 carbon atoms and/or an allyl group having 6 to 18 carbon atoms. 5. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the ether compound is a dialkyl ether. 6. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the amount of the ether compound added is 0.1 to 5 moles per mole of titanium atoms contained in the solid product. 7. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the amount of titanium tetrachloride added is 0.1 to 10 moles per mole of titanium atoms contained in the solid product. 8 The amount of hydrocarbyloxy groups is 0.001 per mole of titanium atoms contained in the solid catalyst component.
A method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the amount is 0.3 mol. 9 The temperature when reducing the titanium compound represented by the general formula Ti (OR ¹ ) _o X _4-o with the organoaluminum compound represented by the general formula A1R ² _n Y _3-n is 10°C to 80°C
A method for producing a solid catalyst component for olefin polymerization according to claim 1.