JPH08120021A - Process for polymerizing alpha-olefin - Google Patents

Abstract

PURPOSE: To obtain an α-olefin polymer having high stereo-regularity and high melt flow. CONSTITUTION: An α-olefin is polymerized in the presence of a catalyst comprising a solid catalyst component essentially consisting of magnesium, titanium, a halogen and an electron donor, an organoaluminum compound component and an organosilicon compound represented by the general formula: R<1> n Si(OR<2> )3-n R<3> (wherein R<1> and R<2> are each a 1-24 C hydrocarbon group; R<3> is a cyclic amino group; and (n) is 0-2).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention uses a highly active catalyst to obtain α
And a method for polymerizing an olefin to produce an α-olefin polymer having high stereoregularity and high melt fluidity.

[0002]

2. Description of the Related Art In recent years, in order to polymerize .alpha.-olefins, a solid catalyst component which requires magnesium, titanium, a halogen element, and an electron donor as an essential component, and an organometallic group I to III metal. A highly active catalyst system comprising a compound and an electron donor as a third component is disclosed in JP-A-57-633.
Many proposals are made in JP-A No. 10-58, JP-A No. 58-83016, JP-A No. 59-58010, and JP-A No. 60-44507. Furthermore, JP-A-62-11705 and JP-A-63-258907
Japanese Patent Laid-Open No. 4-370103 and the like disclose a polymerization catalyst characterized by using a specific silicate as a third component.

Further, JP-A-7-109304 and JP-A-7-11
Japanese Patent No. 8320 discloses a polymerization catalyst using an aminosilane having a specific structure.

Generally, when an α-olefin polymer is produced, in order to improve the melt fluidity of the polymer,
A method of increasing the melt flow rate (MFR) of a polymer by using a chain transfer agent such as hydrogen has been adopted.

However, in the above catalyst system, usually,
Since the melt fluidity of the produced polymer has little dependence on the hydrogen usage of the chain transfer agent, it is necessary to use a large amount of hydrogen in order to improve the melt fluidity. In addition, when the amount of chain transfer agent such as hydrogen is increased to improve the melt flowability of the polymer, generally, the boiling heptane insoluble matter (H.
I.) is greatly reduced.

JP-A-2-84404 and JP-A-4-202505 disclose a catalyst using cyclopentylalkyldimethoxysilane, dicyclopentyldimethoxysilane, di (substituted cyclopentyl) dimethoxysilane, etc. as the third component silicate. A system is disclosed. However, these catalyst systems have a small hydrogen dependence of the melt fluidity of the polymer, which is disadvantageous in obtaining a polymer having a high melt fluidity. In particular, filling a large amount of hydrogen in the bulk polymerization process has a problem of pressure resistance of the device.

Therefore, the various high-activity catalysts described in the above publications are said to be excellent catalysts having high activity and improving the stereoregularity of the polymer, but the polymer having particularly high melt fluidity In order to obtain the above, the above-mentioned drawback becomes a big problem, and its solution is desired.

[0008]

SUMMARY OF THE INVENTION The present invention provides a method for producing an α-olefin polymer having high stereoregularity and high melt fluidity by polymerizing an α-olefin using a highly active catalyst.

[0009]

SUMMARY OF THE INVENTION The present invention provides a catalyst solid component containing magnesium, titanium, a halogen element and an electron donor as component [A], an organoaluminum compound component as component [B], and As the component [C], a compound represented by the general formula R ¹ _n Si (OR ² ) _3-n R ³ (wherein R ¹ and R ² represent a hydrocarbon group having 1 to 24 carbon atoms, and R ³ represents a cyclic amino group) , N is 0 to 2) in the presence of a catalyst consisting of an organosilicon compound represented by the formula: α-olefin polymerization method.

In the present invention, a solid catalyst component containing magnesium, titanium, a halogen element, and an electron donor as essential components is used as the component [A]. The method for producing the catalyst solid component is not particularly limited, and examples thereof include JP-A-54-94590, JP-A-56-55405, JP-A-56-45909, and JP-A-56-163.
102 publication, 57-63310 publication, 57-115408 publication,
58-83006, 58-83016, 58-138707, 59-149905, 60-23404, 60-3.
The methods proposed in JP 2805, JP 61-18330, JP 61-55104, JP-A-2-77413 and JP 2-117905 can be used. As a typical manufacturing method,
(1) A method of co-milling a magnesium compound such as magnesium chloride, an electron donor, and a titanium halide compound such as TiCl ₄ , (2) a magnesium compound and an electron donor are dissolved in a solvent, and the titanium halide is added to this solution. Examples thereof include a method of adding a compound to deposit a catalyst solid.

As the component [A], the catalyst solid components described in JP-A-60-152511, JP-A-61-31402 and JP-A-62-81405 are particularly preferable for achieving the effect of the present invention. preferable. According to the manufacturing method thereof described, tables wherein the aluminum halide (wherein, X ¹ is a halogen.) Represented by AlX ¹ ₃ and, wherein, in _{^{R 4 n Si (OR 5)}} 4-n Silicon compounds
(In the formula, R ⁴ and R ⁵ each represent an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n is an integer of 0 to 3.), and R ⁶ MgX ² A magnesium compound represented by the formula (in the formula, R ⁶ represents an alkyl group having 1 to 8 carbon atoms and X ² represents a halogen atom) is reacted to deposit a solid. As the aluminum halide that can be used in the above reaction, anhydrous aluminum halide is preferable, but it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a small amount of water should also be used. You can Specific examples of aluminum halides include aluminum trichloride, aluminum tribromide and aluminum triiodide, with aluminum trichloride being particularly preferred.

Specific examples of the silicon compound used in the above reaction include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane and dimethyl. Diethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane,
Examples thereof include trimethyl monoethoxysilane and trimethyl monobutoxy silane. In particular, methylphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and dimethyldiethoxysilane are preferable.

The amount of the compound used in the reaction of the aluminum halide with the silicon compound is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3 in terms of element ratio (Al / Si). Preference is given to using active solvents. The reaction temperature is generally 10 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is generally 0.2 to 5 hours, preferably 0.5 to 3 hours.

Specific examples of the magnesium compound used in the above reaction include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, propyl magnesium bromide, butyl magnesium bromide and ethyl. Examples include magnesium iodide. As the solvent of the magnesium compound, for example, an aliphatic ether such as diethyl ether, dibutyl ether, diisopropyl ether, diisoamyl ether, or an aliphatic cyclic ether such as tetrahydrofuran can be used.

The amount of the magnesium compound used is usually 0.5 to 3, preferably 1.5 to 2.3 in terms of the element ratio (Mg / Al) to the aluminum halide used in the preparation of the reaction product of the aluminum halide and the silicon compound. It is a range. The reaction temperature is usually -50 to 100 ° C, preferably-
20 to 50 ° C, reaction time is usually 0.2 to 5 hours, preferably
0.5 to 3 hours.

The white solid obtained in the reaction between the aluminum halide and the silicon compound and subsequently in the reaction with the Grignard compound is contact-treated with an electron donor and a titanium halide compound. As a method of contact treatment,
(1) A method of treating a solid with a titanium halide compound, then treating with an electron donor, and then again treating with a titanium halide compound, and (2) treating the solid with a titanium halide compound and an electron donor. Then, a well-known method such as a method of treating with a titanium halide compound after the treatment with 1 can be adopted. For example, the above solid is dispersed in an inert solvent and the electron donor or / and the titanium halide compound is dissolved therein, or an electron donor or / and a liquid titanium halide compound is used without using an inert solvent. Disperse the solid in. In this case, the contact treatment between the solid and the electron donor or / and the titanium halide compound can be carried out under stirring at a temperature of usually 50 to 150 ° C. and a contact time of 0.2 to 5 hours, although there is no particular limitation. Further, this contact treatment can be performed multiple times.

The titanium halide compound which can be used in the contact treatment is represented by the formula Ti (OR) _p X ³ _4-P (p is an integer of 0 to 3 and X ³ represents a halogen atom). Specific examples include tetrachlorotitanium, tetrabromotitanium, trichloromonobutoxy titanium, tribromomonoethoxy titanium, trichloromonoisopropoxy titanium, dichlorodiethoxy titanium, dichlorodibutoxy titanium, monochlorotriethoxy titanium, monochlorotributoxy titanium. Can be mentioned. Particularly, tetrachlorotitanium and trichloromonobutoxytitanium are preferable.

The electron donor used in the above contact treatment is preferably an aromatic ester, particularly an orthophthalic acid diester. Specific examples of the diester include diethyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, dihexyl orthophthalate, di-2-ethylhexyl orthophthalate, and di-n-heptyl orthophthalate. After the above-mentioned catalytic treatment, the treated solid is generally separated from the treated mixture and thoroughly washed with an inert solvent, and the obtained solid is used as the catalyst solid component [A] of the present invention as an α-olefin polymerization catalyst. be able to.

As the organoaluminum compound as the component [B] of the present invention, alkylaluminum, halogenoalkylaluminum and the like can be used, but alkylaluminum is preferred. Trialkylaluminum is particularly preferable, and specific examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like. Any of the organoaluminum compounds may be used as a mixture. Further, polyaluminoxane obtained by the reaction of alkylaluminum and water can be used as well. The amount of the organoaluminum compound used as the α-olefin polymerization catalyst is 0.1 to 500, preferably 0.5 to 500 in terms of the element ratio (Al / Ti) to titanium of the catalyst solid component [A].
It is 150.

As the component [C] of the present invention, R ¹ _n Si (OR ² ) _3-n R ³ (wherein R ¹ and R ² represent a hydrocarbon group having 1 to 24 carbon atoms, R ^{1 3} represents a cyclic amino group, and n is 0 to 2.) An organosilicon compound represented by the following is used.

Preferred hydrocarbon groups for R ¹ and R ² are:
It is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, and specific examples include methyl, ethyl, propyl and isopropyl. , N-butyl, isobutyl, n-pentyl, n-amyl, n-hexyl, isoamyl,
Examples include cyclopentyl, cyclohexyl, phenyl and octyl groups.

Of these, the most preferable R ¹ is a methyl, ethyl, propyl, isopropyl or isobutyl group,
Most preferred as R ² is a methyl group.

A preferred cyclic amino group for R ³ is
The thing derived from a secondary cyclic amine compound is mentioned. The component (C) of the present invention can be easily obtained by reacting a secondary cyclic amine compound with a silicon halide compound or a Si—O bond-containing silicon compound.

As the silicon halide compound, MeSi (O
Me) ₂ X, EtSi (OMe) ₂ X, PrSi (OMe) ₂ X, Si (OMe) ₃ X (in the formula, X represents a halogen atom) and the like. Si-O
As the bond-containing silicon compound, MeSi (OMe) ₃ , EtSi (OMe
e) ₃ , PrSi (OMe) ₃ , Si (OMe) _{4 and the} like.

As the secondary cyclic amine compound, a pyrrolidine compound, a pyrrole compound, a pyrroline compound, a piperidine compound, a pyridine compound, an indoline compound, an indole compound, a quinoline compound, a carbazole compound,
Examples thereof include ethyleneimine compounds and their derivatives.

Specific examples of the secondary cyclic amine compound include compounds represented by the following formulas.

[0027]

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[0028]

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[0029]

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[0030]

[Chemical 4]

Among the above secondary cyclic amine compounds,
Piperidine, Pyrrolidine
) Is preferred.

As the general formula R ¹ _n Si (OR ² ) _3-n R ³ ,
Is preferably 0 or 1, particularly preferably n is 1, that is, an organosilicon compound represented by the formula R ¹ Si (OR ² ) ₂ R ³ is preferable.

More preferably, the general formula

[0034]

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Examples include methyldimethoxysilane compounds represented by the formula (in the formula, specific examples of R include the following cyclic amino groups).

[0036]

[Chemical 6]

Specific compounds include the following.

Methyl (pyrrolidino) dimethoxysilane (M
PYRDMS), methyl (piperidino) dimethoxysilane (MPI
PDMS), methyl (hexamethyleneimino) dimethoxysilane (MHMIDMS), methyl (2-methylpiperidino) dimethoxysilane (M2MPIPDMS), methyl (3-methylpiperidino) dimethoxysilane (M3MPIPDMS), methyl (4-methylpiperidino) dimethoxysilane (M4MPIPDMS) , Methyl (2,6-dimethylpiperidino) dimethoxysilane (M26DMPI
PDMS), methyl (3,5-dimethylpiperidino) dimethoxysilane (M35DMPIPDMS)

[0039]

[Chemical 7]

Ethyl (piperidino) dimethoxysilane (E
PIPDMS), n-propyl (piperidino) dimethoxysilane
(NPPIPDMS), iso-propyl (piperidino) dimethoxysilane (IPPIPDMS), n-butyl (piperidino) dimethoxysilane (NBPIPDMS), iso-butyl (piperidino) dimethoxysilane (IBPIPDMS), cyclopentyl (piperidino) dimethoxysilane (CPPIPDMS), Cyclohexyl (piperidino) dimethoxysilane (CHPIPDMS)

[0041]

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When the organosilicon compound having a cyclic amino group of the present invention is used, the dependency of the melt fluidity of the produced polymer on the hydrogen of the chain transfer agent becomes large. That is, it has the effect of increasing the melt fluidity with a smaller amount of hydrogen. Therefore, a polymer having a high melt flow rate and a high stereoregularity can be obtained, and in particular, in the bulk polymerization process, the problem of the device pressure resistance due to the filling of a large amount of hydrogen can be improved.

The amount of the component [C] used is the element ratio of the silane of the component [C] to the aluminum of the component [B] (Si / Al).
0.01 to 1 is preferable, and 0.05 to 0.33 is particularly preferable.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used for producing an α-olefin polymer having desired stereoregularity (HI) and melt fluidity (MFR) can be appropriately determined depending on the polymerization method and the polymerization conditions, but usually, Hydrogen partial pressure
It is in the range of 0.05 to 1.0.

In the present invention, during the α-olefin polymerization,
The order of contact of the catalyst components is not particularly limited, but it is not preferable that only the organosilicon compound of the component [C] and the catalyst solid of the component [A] come into direct contact with each other.

Examples of the α-olefin used in the present invention include propylene, 1-butene, 1-hexene, 4-methylpentene-1,1-octene and the like. In the present invention, the above α-olefin can be homopolymerized or copolymerized, and further the above α-olefin and ethylene can be copolymerized. In the present invention, propylene can be homopolymerized, and then ethylene or a mixture of ethylene and propylene can be copolymerized in the presence of the homopolymer to produce a propylene block copolymer.

As the polymerization method in the present invention, a slurry polymerization method using a non-polar solvent such as hexane or heptane, a gas phase polymerization method in which a monomer is brought into contact with a catalyst in a gas state, or a monomer in a liquid state as a solvent is used. A bulk polymerization method or the like in which the polymerization is performed can be adopted. Polymerization pressure is 1
~ 200kg / cm ² , preferably 10 ~ 80kg / cm ² , the polymerization temperature is usually 10 ~ 100 ℃, preferably 30 ~ 90 ℃, the polymerization time is usually
It is in the range of 0.1 to 10 hours, preferably 0.5 to 7 hours.

In the present invention, it is preferable to carry out the main polymerization after prepolymerizing the olefin according to the above-mentioned various polymerization methods. In the pre-polymerization, the catalyst solid component [A] is contact-treated with the organoaluminum compound component [B] and the organosilicon compound component [C] in advance before the main polymerization,
Contact-treated solids can be prepared by washing the solids. Further, using the catalyst solid component [A] or the above-mentioned catalytically treated solid, in the presence of the organoaluminum compound component [B] and the organosilicon compound component [C], a limited amount of α
It is also possible to prepolymerize the olefins. When the contact-treated solid is used, the organosilicon compound component [C] can be omitted in the prepolymerization. By using these contact-treated solids, prepolymerized solids, or washed solids after prepolymerization in the main polymerization, the polymerization activity per catalyst solid and the stereoregularity of the polymer can be improved.

In the present invention, when the above contact-treated solid or prepolymerized solid is used as the catalyst solid component in the main polymerization, the organosilicon compound component [C] can be omitted in the main polymerization.

As the contact treatment of the present invention, the component [A],
The component [B] and the component [C] are mixed and usually 0 to 100
React at 0.1 ℃ for 10 to 10 hours. The order of mixing each component is not particularly limited, but in general, the order of the component [A], the component [B], and the component [C] is preferable. After the contact treatment, the solid is washed with an inert hydrocarbon solvent, filtered and separated to be used as a catalyst solid component in prepolymerization or main polymerization.

The prepolymerization in the present invention can be carried out by a vapor phase method, a slurry method, a bulk method or the like. The solid obtained in the prepolymerization can be separated and then used in the main polymerization, or the main polymerization can be continuously carried out without separation.

The prepolymerization time is usually 0.1 to 10 hours,
It is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the catalyst solid component. Catalyst solid component
If it is less than 0.1 g per 1 g, the main polymerization activity will be insufficient and the amount of catalyst residue will increase, and the stereoregularity of the α-olefin polymer will be insufficient. If it exceeds 100 g, the crystallinity of the α-olefin polymer tends to decrease. The prepolymerization temperature is
It is carried out at 0 to 100 ° C, preferably 10 to 90 ° C in the presence of each catalyst component. When carrying out the prepolymerization at a high temperature exceeding 50 ° C., it is preferable to reduce the α-olefin concentration or shorten the polymerization time. Otherwise catalyst solid component
It is difficult to control the production of 0.1 to 100 g of the prepolymer per 1 g, and the crystallinity of the α-olefin polymer obtained by the main polymerization is lowered.

The amount of the organoaluminum component used in the prepolymerization is usually Al / Ti with respect to the titanium atom of the catalyst solid component.
The molar ratio is 0.5 to 1000, preferably 1 to 100. The amount of the organosilicon compound used is usually 0.01 to Si / Al molar ratio to the aluminum atom of the organoaluminum compound component.
1, preferably 0.1 to 0.5. Further, hydrogen can be allowed to coexist in the preliminary polymerization, if necessary.

[0054]

When an α-olefin is produced using the catalyst of the present invention, an α-olefin polymer having high activity, high stereoregularity of the polymer and high melt flowability can be provided. Due to the large dependence of the melt flowability of the produced polymer on the hydrogen transfer agent of the chain transfer agent, it is possible to obtain a polymer with a high melt flow rate and high stereoregularity, and especially to fill a large amount of hydrogen in the bulk polymerization process. It is possible to reduce the problem of device breakdown voltage.

[Examples] Examples of the present invention will be described below. “Polymerization activity” refers to the yield (g) of the produced polymer per 1 g of the catalyst solid component. Stereoregularity of polymer (HI)
Is the proportion (%) of the rest of the polymer extracted with hot heptane for 20 hours.
Indicates. The melt flowability (MFR) of a polymer represents the weight (g) of the melt polymer measured at 230 ° C. according to ASTM D-1238 under a load of 2.16 kg for 10 minutes.

Polymer melting point (Tm) and crystallization temperature (Tc)
Is DSC (Seiko Denshi Kogyo SSC-5200 DSC-220C)
It measured using. The measurement method is from room temperature to 230 ℃ 10
The temperature was raised at a rate of ° C / min., The temperature was maintained for 5 minutes, then the temperature was lowered from 230 ° C to 40 ° C at a rate of 5 ° C / min, and the crystallization temperature was measured. After that, from 40 ℃ to 230 ℃, 10
The temperature was raised at a rate of ° C / min. And the melting point was measured.

Isopentad Fraction (mmmm)% is Macrom
¹³ C-N attributed based on olelcules 8 , 687 (1975)
It was calculated from the MR spectrum. ^{The 13} C-NMR spectrum was measured using a JEOL EX-400 device, TMS as a reference, and a temperature of 130 ° C. in an o-dichlorobenzene solvent.

Examples 1 to 4 (1) Preparation of solid catalyst component [A] 15 mmol of anhydrous aluminum chloride was added to 40 ml of toluene, and then 15 mmol of methyltriethoxysilane was added dropwise with stirring. After completion of the addition, 25 The reaction was carried out at ℃ for 1 hour. After cooling the reaction product to -5 ° C, 18 ml of diisopropyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction product over 30 minutes with stirring, and the temperature of the reaction solution was adjusted to within the range of -5 to 0 ° C. I kept it. After the dropping was completed, the temperature was gradually raised and the reaction was continued at 30 ° C. for 1 hour. The precipitated solid was filtered off and washed with toluene and n-heptane. Next, 4.9 g of the obtained solid was suspended in 30 ml of toluene, and 150 mmol of titanium tetrachloride and 3.3 mmol of di-n-heptyl phthalate were suspended in this suspension.
Mmol was added, and the mixture was reacted at 90 ° C. for 1 hour with stirring.
The solid was filtered off at the same temperature and washed with toluene and then n-heptane. Furthermore, the solid was suspended again in 30 ml of toluene, 150 mmol of titanium tetrachloride was added, and the mixture was stirred at 90 ° C.
And reacted for 1 hour. The solid was filtered off at the same temperature, and the solid was washed with toluene and then n-heptane. The titanium content in the obtained catalyst solid component was 3.55% by weight. This solid was suspended in 80 ml of heptane to prepare a heptane slurry of catalyst solid components.

(2) Polymerization of Propylene A glass ampoule containing a heptane slurry of a catalyst solid component (7.9 mg as a catalyst solid component) enclosed in an autoclave with an internal volume of 2 L equipped with a stirrer was attached, and then the inside of the autoclave was replaced with nitrogen. . Then triethyl aluminum
2.1 ml of n-heptane solution containing 2.1 mmol was charged to the autoclave. Further, an n-heptane solution containing 0.35 mmol of the silane compound shown in Table 1 as the component [C] 1.
74 ml was charged. Then, after introducing 2.0 kg / cm ² G of hydrogen, 1200 ml of liquid propylene was introduced and the autoclave was shaken. Cool the autoclave to 10 ° C, crush the glass ampoule containing the solid catalyst components with stirring, and
Prepolymerized for minutes. Subsequently, the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out at 70 ° C for 1 hour. After completion of the polymerization, unreacted propylene gas was released, and the polymer was dried under reduced pressure at 50 ° C. for 20 hours to obtain white powdery polypropylene. Table 2 shows the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 5 to 8 As component [C], methyl (piperidino) dimethoxysilane (MPIPDMS) was used, and the amount of hydrogen used (Kg / cm ² ) is shown in Table 3.
The same procedure as in Example 1 was carried out except that the procedure described in 1. was carried out. Tables 3 and 4 show the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 9 to 11 Ethyl (piperidino) dimethoxysilane (EPIPDMS) was used as the component [C], and the amount of hydrogen used (Kg / cm ² ) is shown in Table 5.
The same procedure as in Example 1 was carried out except that the procedure described in 1. was carried out. Tables 5 and 6 show the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 12 to 13 n-propyl (piperidino) dimethoxysilane (NPPIPDMS) was used as the component [C], and the amount of hydrogen used (Kg / cm ² ) was as shown in Table 7, except that The same procedure as in Example 1 was performed. The measurement results of the polymerization activity and the characteristics of the polymer are shown in Tables 7 and 8.

Examples 14 to 15 Iso-propyl (piperidino) dimethoxysilane (IPPIPDMS) was used as the component [C], and the amount of hydrogen used (Kg / cm ² ).
Was carried out in the same manner as in Example 1 except that as shown in Table 7. The measurement results of the polymerization activity and the characteristics of the polymer are shown in Tables 7 and 8.

Examples 16 to 17 Except that n-butyl (piperidino) dimethoxysilane (NBPIPDMS) was used as the component [C] and the amount of hydrogen used (Kg / cm ² ) was as shown in Table 9. The same procedure as in Example 1 was performed. Tables 9 and 10 show the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 18 to 19 Iso-butyl (piperidino) dimethoxysilane (IBPIPDMS) was used as the component [C], and the amount of hydrogen used (Kg / cm ² ) was as shown in Table 9, except that The same procedure as in Example 1 was performed. Tables 9 and 10 show the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 20 to 21 Cyclopentyl (piperidino) dimethoxysilane (CPPIPDMS) was used as the component [C], and the amount of hydrogen used (Kg / c
Example 2 was carried out in the same manner as in Example 1 except that m ² ) was set as shown in Table 11. Tables 11 and 12 show the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 22 to 23 Cyclohexyl (piperidino) dimethoxysilane (CHPIPDMS) was used as the component [C], and the amount of hydrogen used (Kg / c
Example 2 was carried out in the same manner as in Example 1 except that m ² ) was set as shown in Table 11. Tables 11 and 12 show the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 24 to 26 Methyl (pyrrolidino) dimethoxysilane (MPYRPDMS) was used as the component [C], and the amount of hydrogen used (Kg / cm ² ) was shown in Table 1.
The same procedure as in Example 1 was performed except that the procedure described in 3 was used. The measurement results of the polymerization activity and the characteristics of the polymer are shown in Tables 13 and 14.

Examples 27 to 28 Methyl (hexamethyleneimino) dimethoxysilane (MHMIDMS) was used as the component [C], and the amount of hydrogen used (Kg / c
Example 1 was repeated except that m ² ) was changed as shown in Table 13. The measurement results of the polymerization activity and the characteristics of the polymer are shown in Tables 13 and 14.

Examples 29 to 34 As component [C], methyl (4-methylpiperidino) dimethoxysilane (M4MPIPDMS) [Example 29], methyl (3-
Methylpiperidino) dimethoxysilane (M3MPIPDMS) [Example 30], Methyl (2-methylpiperidino) dimethoxysilane (M2MPIPDMS) [Examples 31 to 32], Methyl (3,3,2)
5-Dimethylpiperidino) dimethoxysilane (M35MPIPDMS)
[Example 33], methyl (2,6-dimethylpiperidino) dimethoxysilane (M26MPIPDMS) [Example 34] was used, and the amount of hydrogen used (Kg / cm ² ) was changed as shown in Table 15. Was performed in the same manner as in Example 1. Tables 15 and 16 show the measurement results of the polymerization activity and the characteristics of the polymer.

Comparative Examples 1 to 4 Same as Example 1 except that cyclohexylmethyldimethoxysilane (CMDMS) was used as the component [C] and the amount of hydrogen used (Kg / cm ² ) was as shown in Table 17. I went to.
The measurement results for the polymerization activity and the properties of the polymer are shown in Table 1.
7 and Table 18.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

[Table 10]

[0082]

[Table 11]

[0083]

[Table 12]

[0084]

[Table 13]

[0085]

[Table 14]

[0086]

[Table 15]

[0087]

[Table 16]

[0088]

[Table 17]

[0089]

[Table 18]

[Brief description of drawings]

FIG. 1 is a flow chart showing a preparation process and a polymerization method of a catalyst component of the present invention.

Front page continued (72) Inventor Jun Yamashita 8-1 Goi Minamikaigan, Ichihara City, Chiba Ube Industries Ltd. Chiba Research Institute

Claims (1)

[Claims] 1. A catalyst solid component essentially comprising magnesium, titanium, a halogen element, and an electron donor as component [A], an organoaluminum compound component as component [B], and a general formula R ¹ _n as component [C]. Si (OR ² ) _3-n R ³ (In the formula, R ¹ and R ² represent a hydrocarbon group having 1 to 24 carbon atoms, R ³ represents a cyclic amino group, and n is 0 to 2.) A method for polymerizing an α-olefin, which comprises polymerizing an α-olefin in the presence of a catalyst consisting of an organosilicon compound represented by