JPS6251282B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for stereoregular polymerization of α-olefins, and more specifically, the present invention relates to a method for stereoregular polymerization of α-olefins, and more specifically, a method for stereoregular polymerization of α-olefins using a catalyst comprising a specific activated titanium catalyst component and an organoaluminum compound.
-Relates to a method for polymerizing olefins to obtain highly stereoregular poly-α-olefins with high activity.

In recent years, the method of polymerizing ethylene using a catalyst consisting of a titanium catalyst component in which titanium is supported on a magnesium compound and an organoaluminum compound has become common, but propylene, butene-
Regarding the polymerization of α-olefins such as No. 1, it is difficult to obtain a useful crystalline polymer if not only the polymerization activity of the catalyst but also the alkyl groups such as methyl groups and ethyl groups are sterically controlled to form an isotactic structure. Can not. Therefore, controlling the polymerization activity of the catalyst as well as the stereoregularity of the produced polymer has become a major problem. However, in general, there is an inverse correlation between the polymerization activity of the catalyst and the stereoregularity of the resulting polymer, and it is difficult to maintain both at the same time. It is hard to say that it is sufficient.

The present inventors have conducted intensive research to develop a method that can overcome the drawbacks of the above-mentioned conventional techniques and maintain a high degree of both polymerization activity and stereoregularity of the resulting polymer.As a result, the inventors have developed a specially treated magnesium compound. discovered that the objective could be achieved by using a titanium component supported on the catalyst as a component of the catalyst,
The present invention has now been completed.

That is, the present invention provides a method for producing a poly-α-olefin having stereoregularity by polymerizing α-olefin using a catalyst comprising a reaction product of A magnesium compound and a titanium compound and B an organoaluminum compound. , in the first step ^{, the} general formula Mg ⁽ OR ¹ _{) o} 2.0) in the presence or absence of an organic acid ester.
(OR ² ) _n X ² _4-n (R ² is an alkyl group having 1 to 10 carbon atoms,
Indicates a cycloalkyl group or an aryl group, X ²
represents a halogen atom, and m represents 0 to 3.0. ) and an alcohol represented by the general formula R ³ OH (R ³ represents an alkyl group or a cycloalkyl group having 1 to 10 carbon atoms), and then as a second step, the above-mentioned The solid material produced in one step can be used as is or after pretreatment with an organic acid ester, in the presence or absence of an organic acid ester (however, if an organic acid ester has not been used in the process up to this point, it must be present). .) with a single carrier formula Ti( ^OR4 ) _{lX34 -l} ^{( R4} represents an alkyl group, cycloalkyl group, or aryl group having 1 ^to 10 carbon atoms, Provided is a method for the stereoregular polymerization of α-olefin, characterized in that a solid product obtained by reacting with a halogen-containing tetravalent titanium compound represented by (3.0) is used as component A of the catalyst. It is something to do.

The magnesium compound used in the present invention has the general formula
It is expressed as Mg(OR ¹ ) _o X ¹ _2-o . Here, R ¹ represents a linear or side-chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group. Further, X ¹ represents a halogen atom such as chlorine or bromine, and n represents a real number between 1.0 and 2.0. Specific examples of this magnesium compound include magnesium dialkoxide such as magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium monochloromonomethoxide, magnesium monochloromonoethoxide, magnesium monochloromonopropoxide, etc. Examples include magnesium monohalogenated monoalkoxide.

Next, the halogen-containing silicon compound used in the present invention is represented by the general formula Si(OR ² ) _n X ² _4-n . Here, R ² is an alkyl group having 1 to 10 carbon atoms,
Indicates a cycloalkyl group or an aryl group. Further, X ² represents a halogen atom such as chlorine or bromine, and m represents a real number between 0 and 3.0. in particular
SiCl ₄ , CH ₃ OSiCl ₃ , (CH ₃ O) ₂ SiCl ₂ ,
(CH ₃ O) ₃ SiCl, C ₂ H ₅ OSiCl ₃ , (C ₂ H ₅ O) ₂ SiCl ₂ ,
(C ₂ H ₅ ) ₃ SiCl, C ₃ H ₇ OSiCl ₃ , (C ₃ H ₇ O) ₂ SiCl ₂ ,
(C ₃ H ₇ O) ₃ SiCl, C ₆ H ₅ OSiCl ₃ , (C ₆ H ₅ O) ₂ SiCl ₂ ,
Examples include (C ₆ H ₅ O) ₃ SiCl, and these may be used alone or as a mixture. Among these, it is particularly preferable to use silicon tetrachloride (SiCl ₄ ).

Furthermore, the alcohol used in the present invention has the general formula
It is represented by R ³ OH, and R ³ is an alkyl group or a cycloalkyl group having a linear or side chain having 1 to 10 carbon atoms. Specific examples of the alcohol include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, octanol, and cyclohexanol.

The preparation of component A of the catalyst used in the method of the present invention is carried out in two steps. In the first step, the above-mentioned magnesium compound, halogen-containing silicon compound, and alcohol are added to an inert solvent and heated to a predetermined temperature. The magnesium compound is denatured by carrying out a contact reaction while stirring for , hours. At this time, it is also effective to have an organic acid ester present in the reaction system. In addition, the above reaction is usually carried out at a reaction temperature of -10 to 150
C., preferably 20 to 100.degree. C., is efficient and preferred because the resulting catalyst has high polymerization activity. Although the reaction time depends on the reaction temperature, it may be appropriately selected in the range of usually 5 minutes to 5 hours, preferably 30 minutes to 3 hours. The order in which the magnesium compound, halogen-containing silicon compound, and alcohol are brought into contact with each other in this reaction is not particularly limited, and they may be added to an inert solvent at the same time and reacted. First, the magnesium compound and the halogen-containing silicon compound are reacted. Then, alcohol may be added and reacted. Furthermore, the ratio of addition of the above three substances varies depending on the type of compound used, reaction conditions, etc., and may be determined as appropriate, but generally the halogen-containing silicon compound is added to the magnesium compound at least 0.01 times in mole, preferably The alcohol should be 0.05 to 5 times the molar amount of the magnesium compound.
It should be at least 0.01 times the mole, preferably 0.05 to 5 times the mole. If a large amount of this halogen-containing silicon compound is added, the polymerization activity of the resulting catalyst will not be sufficiently improved, and conversely, if the amount added is too small, the polymerization activity of the catalyst will still be insufficient, and furthermore, the polymerization activity of the catalyst will be insufficient. The stereoregularity of the polymer also becomes unsatisfactory. Furthermore, if the amount of alcohol added is too small, a sufficient improvement in the polymerization activity of the catalyst cannot be expected.

The solvent used in the above-mentioned catalytic reaction is not particularly limited as long as it is inert and does not react with the above-mentioned magnesium compound, halogen-containing silicon compound, and alcohol, and various solvents such as aliphatic hydrocarbons and alicyclic hydrocarbons may be used. can give. Specific examples include pentane, hexane, n-heptane, and cyclohexane. Although the reaction using these solvents is a preferred embodiment of the present invention, it is also possible to carry out the reaction without a solvent. In this case, for example, a predetermined ratio of the magnesium compound, halogen-containing silicon compound, and alcohol may be mixed and reacted directly mechanically using a ball mill or the like.

Furthermore, the above-mentioned contact reaction is carried out in the presence or absence of an organic acid ester. When the organic acid ester is present in the reaction system, there is no particular restriction on the timing of addition, and it may be added before or simultaneously with the addition of each of the above compounds, or after the addition of each compound. Various organic acid esters can be used here, such as methyl formate, n-butyl formate, ethyl acetate, n-amyl acetate, vinyl acetate,
Aliphatic carboxylic acid esters such as benzyl acetate, cyclohexyl acetate, methyl acrylate, methyl methacrylate, or methyl benzoate, ethyl benzoate, n-propyl benzoate, i-propyl benzoate, n-butyl benzoate, i-benzoate -butyl, sec-butyl benzoate, tert-butyl benzoate, n-amyl benzoate, i-amyl benzoate,
Aromatic carboxylic acid esters such as methyl toluate, ethyl toluate, n-butyl toluate, i-butyl toluate, sec-butyl toluate, and tert-butyl toluate can be mentioned.

When the organic acid ester is present in the first-stage reaction system, the amount to be present is 0.01 times the mole or more, preferably 0.05 to 10 times the amount of the magnesium compound. If the organic acid ester is present within this range, the polymerization activity will be high and the stereoregularity of the obtained polymer will also be high.

In the present invention, the solid material, which is a modified magnesium substance obtained in the above-mentioned first-stage contact reaction, is further treated in the second stage.
In this second step, the solid material obtained in the first step, after washing or unwashed, is prepared with the general formula Ti(OR ⁴ ) _l X ³ _4-l in the presence or absence of an organic acid ester. React with a halogen-containing tetravalent titanium compound. Here, R ⁴ is an alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms,
X ³ is a halogen atom such as chlorine or bromine, and l is a real number between 0 and 3.0. This halogen-containing 4
Specific examples of titanium compounds include TiCl ₄ ,
Examples include titanium tetrahalides such as TiBr ₄ , CH ₃ OTiCl ₃ , (C ₂ H ₅ O) ₂ TiCl ₂ and alkoxy titanium halides, and these may be used alone or as a mixture. Among these, it is preferable to use a material containing a high halogen content, and it is particularly preferable to use titanium tetrachloride (TiCl ₄ ).

Prior to this second step, the solid material produced in the first step may be pretreated with an organic acid ester, and then subjected to the second step reaction.
The organic acid ester used in this pretreatment may be the same as those mentioned above, or may be different. In addition, this pretreatment may be carried out by directly adding the organic acid ester to the solid substance and co-pulverizing it, or by adding the solid substance and the organic acid ester to a solvent such as pentane, hexane, heptane, octane, etc. and performing a slurry reaction. You may do so. The reaction temperature is -10~150℃, preferably 10~100℃
It should be ℃. In the case of co-pulverization, the reaction should be carried out for at least 0.5 hours at room temperature, while in the case of slurry reaction, the reaction should be carried out for 5 minutes to 5 hours, preferably 30 minutes to 3 hours. Furthermore, after the reaction, in the case of co-pulverization, a hydrocarbon such as pentane, hexane, heptane, octane, etc. is added to precipitate the solid material, and the precipitated solid material is subjected to the second stage reaction, either washed or unwashed. Further, in the case of a slurry reaction, it is used as it is or after washing, it is subjected to the second stage reaction.

Furthermore, the second stage reaction system has the general formula Si
(OR ⁵ ) _k X ^{4 4} _-k (R ⁵ represents an alkyl group, aralkyl group, or aryl group having 1 to 10 carbon atoms; It is also effective to add the silicon compounds shown. Specifically, this silicon compound is SiCl ₄ ,
_{CH3SiCl3 , CH3OSiCl3 ,} ( _CH3 ) _{2SiCl2 ,}
(CH ₃ O) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, (CH ₃ O) ₃ SiCl,
(CH ₃ ) ₄ Si, (CH ₃ O) ₄ Si, C ₂ H ₅ SiCl ₃ ,
C ₂ H ₅ OSiCl ₃ , (C ₂ H ₅ ) ₂ SiCl ₂ , (C ₂ H ₅ O) ₂ SiCl ₂ ,
(C ₂ H ₅ ) ₃ SiCl, (C ₂ H ₅ O) ₃ SiCl, (C ₂ H ₅ ) ₄ Si,
(C ₂ H ₅ O) ₄ Si, C ₃ H ₇ SiCl ₃ , C ₃ H ₇ OSiCl ₃ ,
(C ₃ H ₇ ) ₂ SiCl ₂ , (C ₃ H ₇ O) ₂ SiCl ₂ , (C ₃ H ₇ ) ₃ SiCl,
(C ₃ H ₇ O) ₃ SiCl, (C ₃ H ₇ ) ₄ Si, (C ₃ H ₇ O) ₄ Si,
C ₆ H ₅ SiCl ₃ , C ₆ H ₅ OSiCl ₃ , (C ₆ H ₅ ) ₂ SiCl ₂ ,
(C ₆ H ₅ O) ₂ SiCl ₂ , (C ₆ H ₅ ) ₃ SiCl, (C ₆ H ₅ O) ₃ SiCl,
Examples include (C ₆ H ₅ ) ₄ Si and (C ₆ H ₅ O) ₄ Si.

Moreover, this second step is carried out in the presence or absence of an organic acid ester. However, if the organic acid ester has never been involved in the process up to this point, that is, if the organic acid ester is not used in the first step and the obtained solid material is not pretreated, the second step must be An organic acid ester must be present. In other words, in the method of the present invention, an organic acid ester is present in the reaction system of either or both of the first stage and the second stage, or the solid material obtained in the first stage is pretreated with an organic acid ester. is necessary. The organic acid ester to be present in the reaction system of this second stage may be the same type as that used in the first stage or pretreatment described above, such as aliphatic carboxylic ester,
An aromatic carboxylic acid ester or the like may be used as appropriate.

The addition ratio of the halogen-containing tetravalent titanium compound, silicon compound, and organic acid ester used in the second step of the present invention may vary depending on the type of compound used, reaction conditions, etc., and may be determined as appropriate. The content of the tetravalent titanium compound should be 0.1 to 100 times the mole of the above-mentioned magnesium compound, preferably 0.5 to 50 times the mole, and the silicon compound should be 0 to 5 times the mole of the magnesium compound, preferably 2 times the mole. The organic acid ester should be less than 0.01 molar relative to the magnesium compound.
It should be 10 times molar, preferably 0.05 to 5 times molar.

If the addition ratio exceeds the above, the polymerization activity of the resulting catalyst will not be sufficiently improved, and the stereoregularity of the resulting polymer will also be unsatisfactory.

The order of addition of each compound in the second step reaction of the present invention is not particularly limited, and for example, (a) a method of simultaneously adding a halogen-containing tetravalent titanium compound and an organic acid ester to the solid material obtained in the first step ( (However, no silicon compound is added.) (b) A method in which the solid material obtained in the first step is pretreated by adding an organic acid ester, and then a halogen-containing tetravalent titanium compound is added (however, no silicon compound is added. (c) A method in which the solid material obtained in the first step is first pretreated by adding an organic acid ester, and then a halogen-containing tetravalent titanium compound and a silicon compound are added (d) The solid material obtained in the first step is pretreated. A method of pre-treating the obtained solid material by adding a silicon compound and an organic acid ester, and then adding a halogen-containing tetravalent titanium compound (e) A method in which a halogen-containing tetravalent titanium compound, Various methods can be considered, such as a method of adding a silicon compound and an organic acid ester at the same time.

The second step of the method of the present invention is carried out in the order described above, but usually the reaction is carried out in a liquid phase of a halogen-containing tetravalent titanium compound or in an inert solvent such as pentane, hexane, n-heptane, or cyclohexane. The temperature is 20 to 200°C, preferably 50 to 150°C, and the reaction time is 5 minutes to 10 hours, preferably 30 minutes to 5 hours.

In the present invention, the solid product obtained by this second step reaction is washed with an inert hydrocarbon such as pentane, hexane, cyclohexane, n-heptane, etc. as necessary, and the solid product after washing is Used as component A (solid catalyst component) of an α-olefin polymerization catalyst.

The method of the present invention uses the above solid product as component (A) and an organoaluminum compound as component B.
α-olefin is polymerized using a catalyst consisting of both components A and B.

In the polymerization of α-olefin, a dispersion of component A and an organoaluminum compound as component B are added as catalysts to the reaction system, and if necessary, a compound containing nitrogen, oxygen, phosphorus, or sulfur, such as an ester , an electron-donating compound such as an ether, and then an α-olefin is introduced into the system.
The polymerization method and conditions are not particularly limited, and slurry polymerization using an inert hydrocarbon solvent, liquid phase polymerization without a solvent, gas phase polymerization, etc. are possible.
Further, both continuous polymerization and discontinuous polymerization are possible. For example, in the case of slurry polymerization using an inert hydrocarbon solvent or liquid phase polymerization without a solvent, the amount of the catalyst component added is 0.001 to 10 mmol/, preferably 0.005 to 10 mmol/A component converted to titanium atoms.
5 mmol/. On the other hand, the proportion of component B to the titanium atoms in component A is 1 to 1000 (mole ratio), preferably 10 to 500 (molar ratio). Further, the amount of the electron donating compound added should be 0 to 500 (mole ratio), preferably 5 to 200 (mole ratio) to the titanium atoms of component A. The α-olefin pressure in the reaction system is preferably normal pressure to 50 kg/cm ² , and the reaction temperature is 0.
-200°C, preferably 30-100°C is suitable. Molecular weight adjustment during polymerization can be carried out by known means, such as hydrogen. The reaction time may be appropriately selected from 5 minutes to 10 hours, preferably from 30 minutes to 5 hours.

Examples of organoaluminum compounds which are component B of the catalyst used in the method of the present invention include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum, and diethylaluminum monochloride and diisopropylaluminum monochloride. Dialkylaluminum monohalides such as chloride, diisobutylaluminum monochloride, dioctylaluminum monochloride are preferred, and mixtures thereof can also be used.

The α-olefin that can be polymerized by the method of the present invention is usually one represented by the general formula R ⁶ -CH=CH ₂ (R ⁶ represents hydrogen or an alkyl group having 1 to 6 carbon atoms), such as ethylene, propylene, etc. , butene-
Examples include linear monoolefins such as 1, hexene-1 and octene-1, and branched monoolefins such as 4-methyl-pentene-1. Furthermore, according to the method of the present invention, it is also possible to polymerize dienes such as butadiene and various other types.

The method of the present invention can be effectively used for homopolymerization of these or copolymerization of various α-olefins.

According to the method of the present invention, the catalyst used has extremely high activity and the resulting polymer has high stereoregularity, so that the product value is extremely high.

Therefore, since the method of the present invention is highly active polymerization, the catalyst removal step and the polymer washing step can be simplified or omitted, and very efficient polymerization can be carried out.

Next, examples of the present invention will be shown. Note that all operations in the following examples were performed under an argon stream.

Example 1 [Production of solid catalyst component] Dehydrated hexane in a 500 ml four-necked flask
A solution of 1.9 ml of isopropanol and 10 ml of hexane was added dropwise from the dropping funnel at room temperature over 1 hour, the temperature was raised, and the reaction was carried out under reflux for 2 hours. Summer. Then bring to room temperature and add 50 ml of ethyl benzoate.
was added dropwise, and the reaction was carried out for 1.5 hours at room temperature.
Wash the generated solid three times with 200 ml of n-heptane, add 100 ml of titanium tetrachloride, and heat at 135°C.
The reaction was carried out for 2.5 hours. After the reaction was completed, washing was repeated with n-heptane using a decanting method to obtain a solid catalyst component. When the amount of titanium supported was measured by a colorimetric method, it was 22 mg-Ti/g-support.

[Polymerization of propylene]

1 In a stainless steel autoclave, 400 ml of n-heptane, 2.0 mmol of triethylaluminum,
The solid catalyst component is 0.02 mmol as Ti, p-
0.40 mmol of methyl toluate was added and the temperature was raised to 70°C. Polymerization was carried out for 2 hours by continuously supplying propylene at 7 kg/cm ² . Unreacted propylene was purged to obtain a white polymer.
The yield was 138g. The catalytic activity of this product was equivalent to 144 kg per gram of titanium atom. In addition, when this polymer was extracted with boiling n-heptane for 6 hours using a Soxhlet extractor,
The extraction residue was 95.2%, and the amount of polymer soluble in the polymerization solvent was 5.3 g.

Example 2 [Production of solid catalyst component] In Example 1, after the reaction under reflux for 2 hours, the reaction product was converted to n- before adding ethyl benzoate.
A solid catalyst component was obtained under the same conditions except that it was washed three times with 200 ml of heptane. The amount of titanium supported is 32
mg-Ti/g-carrier.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1, except that 0.02 mmol of the solid catalyst component obtained above was used as Ti and 0.35 mmol of methyl p-toluate, to obtain 154.3 g of polymer.
The catalytic activity of this product is 161 per gram of titanium atom.
It was equivalent to Kg. When this polymer was extracted with boiling n-heptane using a Soxhlet extractor for 6 hours, the extraction residue was 94.5% and the amount of polymer soluble in the polymerization solvent was 7.1 g.

Example 3 [Production of solid catalyst component] 1.5 ml of ethanol instead of isopropanol
A solid catalyst component was obtained under the same conditions as in Example 1 except that . The amount of titanium supported is 19mg−
It was Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 151g. The catalytic activity of this product was 157 kg per gram of titanium atom. In addition, the residue extracted from this polymer with boiling n-heptane was 93.8
%, and the amount of polymer soluble in the polymerization solvent was 7.1 g.

Example 4 [Production of solid catalyst component] Instead of silicon tetrachloride (SiCl ₄ ), Si
A solid catalyst component was obtained under the same conditions as in Example 1 except that 5.9 ml of (OC ₂ H ₅ ) ₃ Cl was used. The amount of titanium supported was 20 mg-Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 101g. The catalytic activity of this product was 105 kg per gram of titanium atom. In addition, the residue extracted from this polymer with boiling n-heptane was 93.6
%, and the amount of polymer soluble in the polymerization solvent was 6.9 g.

Reference Example 1 [Production of solid catalyst component] A solid catalyst component was obtained under the same conditions as in Example 1 except that isopropanol was not used. The amount of titanium supported was 39 mg-Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 119g. The catalytic activity of this product was 124 kg per gram of titanium atom. In addition, the residue extracted from this polymer with boiling n-heptane is 78.9
%, and the amount of polymer soluble in the polymerization solvent was 25.2 g.

Reference Example 2 [Manufacture of solid catalyst component] A solid catalyst component was obtained under the same conditions as in Example 1 except that silicon tetrachloride was not used. The amount of titanium supported was 18 mg-Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 18g. The catalytic activity of this product was 19 kg per gram of titanium atom. Further, the residual amount of this polymer after extraction with boiling n-heptane was 78.1%, and the amount of polymer soluble in the polymerization solvent was 6.0 g.

Example 5 [Production of solid catalyst component] Dehydrated hexane in a 2-volume four-necked flask
900 ml and 60 g of magnesium diethoxide were charged and stirred. This is then added to silicon tetrachloride at room temperature.
Added 15.1ml. Next, 15.1ml of isopropyl alcohol was added dropwise from the dropping funnel over 30 minutes, and then
The temperature was raised to 70°C and the reaction was carried out for 2 hours. Thereafter, the resulting slurry was filtered and washed three times with dry hexane to obtain a solid.

Further, 20 g of the above solid was ground with 60 ml of ethyl benzoate in a ball mill at room temperature for 15 hours. 30g of the obtained viscous liquid was mixed with n-heptane 250g at room temperature.
ml, a solid precipitated out. Next, the solid was separated, washed twice with 250 ml of n-heptane, and then dried under reduced pressure. Next, this solid was suspended in 150 ml of titanium tetrachloride, and a reaction was carried out at 80°C for 2.5 hours. After the reaction was completed, washing was repeated with n-heptane using a decanting method to obtain a solid catalyst component. The amount of titanium supported is 36 mg−
It was Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1, except that 0.3 mmol of methyl p-toluate was used. The yield was 152g. The catalytic activity of this product was 158 kg per gram of titanium atom. Further, the residue of this polymer after extraction with boiling n-heptane was 93.8%, and the amount of polymer soluble in the polymerization solvent was 5.0 g.

Example 6 [Production of solid catalyst component] Dehydrated hexane in a 500 ml four-neck flask
150 ml, 7.5 g of magnesium diethoxide, and 1.9 ml of silicon tetrachloride were added, and a solution of 1.9 ml of isopropanol and 10 ml of n-hexane was added dropwise from the dropping funnel at room temperature over 1 hour, followed by 28 ml of ethyl benzoate.
After dropping, the reaction was carried out at 30°C for 1.5 hours. The produced solid was washed three times with 200 ml of n-heptane, 100 ml of titanium tetrachloride was added, and the reaction was carried out under boiling for 2.5 hours. After the reaction was completed, washing was repeated with n-heptane using a decanting method to obtain a solid catalyst component. When the amount of titanium supported was measured by a colorimetric method, it was 36 mg-Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 60g. The catalytic activity of this product was 63 kg per gram of titanium atom. Further, the residual amount of this polymer after extraction with boiling n-heptane was 95.0%, and the amount of polymer soluble in the polymerization solvent was 3.0 g.

Example 7 [Production of solid catalyst component] Dehydrated hexane in a 500 ml four-necked flask
A solution of 1.9 ml of isopropanol and 10 ml of hexane was added dropwise from the dropping funnel at room temperature over 1 hour, the temperature was raised, and the reaction was carried out under reflux for 2 hours. Summer. The resulting solid was washed three times with 200 ml of n-heptane, then brought to room temperature, 28 ml of ethyl benzoate and 100 ml of titanium tetrachloride were added, and the reaction was carried out under boiling for 2.5 hours. After the reaction was completed, washing was repeated with n-heptane using a decanting method to obtain a solid catalyst component. When the amount of titanium supported was measured by a colorimetric method, it was 42 mg-Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 70g. The catalytic activity of this product was 73 kg per gram of titanium atom. Further, the residual amount of this polymer after extraction with boiling n-heptane was 94.3%, and the amount of polymer soluble in the polymerization solvent was 3.5 g.

Example 8 [Production of solid catalyst component] In Example 1, ethylmagnesium chloride (C ₂ H ₅ MgCl) was added to the tetrahydrofuran solvent,
Reacting magnesium and equimolar ethanol,
A solid catalyst component was obtained under the same conditions except that 6.9 g of ethoxymagnesium chloride Mg(OC ₂ H ₅ )Cl obtained by drying under reduced pressure was used instead of magnesium diethoxide. The amount of titanium supported is 16 mg−
It was Ti/g-support.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the above-mentioned solid catalyst component was used.
The yield was 122g. The catalytic activity of this product was 127 kg per gram of titanium atom. In addition, the residue extracted from this polymer with boiling n-heptane was 95.1
%, and the amount of polymer soluble in the polymerization solvent was 11.3 g.

[Brief explanation of the drawing]

FIG. 1 is a drawing showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1. Polymerizing an α-olefin using a catalyst containing a reaction product of A a magnesium compound and a titanium compound and an organoaluminum compound B to produce a polyα-olefin having stereoregularity. In the method, as a first step the general formula Mg
(OR ¹ ) _o X ¹ _2-o (R ¹ is an alkyl group having 1 to 10 carbon atoms,
Indicates a cycloalkyl group or an aryl group, X ¹
represents a halogen atom, and n represents 1.0 to 2.0. )
In the presence or absence of an organic acid ester, a magnesium compound represented by the general formula Si
(OR ² ) _n X ² _4-n (R ² is an alkyl group having 1 to 10 carbon atoms,
Indicates a cycloalkyl group or an aryl group, X ²
represents a halogen atom, and m represents 0 to 3.0. ) and an alcohol represented by the general formula R ³ OH (R ³ represents an alkyl group or a cycloalkyl group having 1 to 10 carbon atoms), and then as a second step, the above-mentioned The solid material produced in one step may be used as it is or after being pretreated with an organic acid ester, in the presence or absence of the organic acid ester (however, if the organic acid ester has not been used in the process up to this point, it must be present. ) ^with _a ^single carrier Ti (OR ⁴ ₎ ^l A method for stereoregular polymerization of α-olefins, characterized in that a solid product obtained by reacting with a halogen-containing tetravalent titanium compound represented by the following is used as component A of the catalyst. 2 α-olefin has the general formula R ⁶ −CH=CH ₂ (R ⁶
represents hydrogen or an alkyl group having 1 to 6 carbon atoms. ) The method according to claim 1, wherein the method is represented by: 3. The method according to claim 1, wherein the α-olefin is propylene. 4. The method according to claim 1, wherein the organic acid ester is an aliphatic carboxylic ester or an aromatic carboxylic ester. 5. The method according to claim 1, wherein the halogen-containing silicon compound is silicon tetrachloride. 6. The method according to claim 1, wherein the halogen-containing tetravalent titanium compound is titanium tetrachloride.