JP3215691B2 - Method for producing olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for producing an olefin polymer. More specifically, the present invention relates to highly stereoregular olefin polymers,
The present invention relates to a method for producing an olefin polymer having a high stereoregularity and a wide molecular weight distribution in a high yield.

[0002]

2. Description of the Related Art Conventionally, in the production of olefin polymers, olefins have been widely polymerized using a Ziegler catalyst. In order to obtain a highly active catalyst or a polymer having a high stereoregularity, various attempts have been made to improve the Ziegler catalyst.

For example, in order to improve the stereoregularity of an olefin polymer, a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, an organoaluminum compound, and an organosilicon having a Si—O—C bond A method of polymerizing an α-olefin having 3 or more carbon atoms using a catalyst comprising a combination with a compound has been proposed (JP-A-57-63310 and JP-A-57-63311).
No. gazette. ). However, these methods are not always satisfactory enough to obtain a high stereoregular polymer in a high yield, and further improvement has been desired.

As a method for obtaining a high stereoregular polymer in a high yield, an organoaluminum compound and a Si—O—C are added to a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor as described above. Olefin polymerization method using a catalyst in combination with an organosilicon compound having a bond (JP-A-54-94590), and olefin polymerization using a compound having a branched chain hydrocarbon residue as the organosilicon compound Method (JP-A-62-11)
No. 706) is disclosed. However,
In these methods, although a high stereoregular polymer is obtained in a high yield, the polymer has a narrow molecular weight distribution and is inferior in moldability, and when molding a large molded product, a desired rigidity is hardly exhibited. There is a disadvantage that.

[0005]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an olefin polymer for obtaining a polymer having high stereoregularity and a wide molecular weight distribution in high yield. The purpose of the present invention is to provide a manufacturing method.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a solid catalyst component comprising magnesium compound, titanium halide and electron donating compound as essential components as a catalyst. It has been found that by using a combination of an organoaluminum compound and a dialkyldialkoxysilane having a specific structure, a polymer having high stereoregularity and a wide molecular weight distribution can be obtained in high yield. Based on this finding, the present invention has been completed.

That is, the present invention according to claim 1 provides (A)
(a) Reaction of metal magnesium with alcohol and halogen
The product is a magnesium compound, (b) a titanium halide and (c) a solid catalyst component having an electron-donating compound as an essential component, (B) an organoaluminum compound, and (C) a general formula (II)

[0008]

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Wherein R ⁴ is a hydrocarbon residue in which the carbon atom adjacent to Si is a tertiary carbon atom, and R ⁵ is a straight-chain or branched-chain hydrocarbon residue. The present invention provides a method for producing an olefin polymer, which comprises contacting an olefin with a catalyst comprising a combination with an organosilicon compound to polymerize the catalyst.

The present invention according to claim 2 provides (A) and (a)
Gnesium compound, (b) titanium tetrachloride, and (c) electron donation
Solid catalyst component obtained by contacting the reactive compound with (B)
An organoaluminum compound, (C) a general formula (III)

[0011]

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(Wherein, R ⁶ is a branched hydrocarbon residue, R ⁷
Is a cyclic saturated hydrocarbon residue, R ⁸ is a linear or branched carbon
It is a hydride residue. With an organosilicon compound represented by
The olefin is brought into contact with the catalyst
To provide a method for producing an olefin polymer.
To offer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, a catalyst used in the method of the present invention according to claim 1 will be described.
Will be described. Use in the method of the invention according to claim 1
The catalyst consists of (A) (a) metallic magnesium, alcohol and halogen
Magnesium compound which is a reaction product with
Titanium Genide and (c) an electron donating compound as essential components
Solid catalyst component, (B) an organoaluminum compound, and (C)
From the combination with the organosilicon compound represented by the general formula (II)
Catalyst. In the method of the present invention according to claim 1,
The component (A) of the catalyst, that is, the solid catalyst component, comprises (a) a metal matrix.
The reaction product of gnesium, alcohol and halogen
Magnesium compound, (b) titanium halide and (c)
An electron-donating compound is an essential component.

In the present invention according to claim 1, the (a)
As a component magnesium compound, metal magnesium and
Magnesium, a reaction product of alcohol and halogen
Use a compound. In this case, catalytic activity, stereoregularity,
The amount of titanium carried is further improved, and a polymer powder having better morphology is obtained. There is no particular limitation on the shape of the metallic magnesium used at this time, and metallic magnesium of any shape, for example, granular,
Any of a ribbon shape and a powder shape can be used. There is no particular limitation on the surface state of the metallic magnesium, but it is advantageous that the surface of the metallic magnesium has no coating such as magnesium oxide.

The alcohol in the reaction product of the metal magnesium, the alcohol and the halogen is not particularly limited, but is preferably a lower alcohol having 1 to 6 carbon atoms, and particularly preferably ethanol is a solid catalyst which improves the catalytic performance. It is preferred because it provides components. The purity and water content of this alcohol are not particularly limited, but when an alcohol having a high water content is used, magnesium hydroxide is formed on the surface of the metal magnesium.
In the following, it is particularly preferable to use an alcohol of 2000 ppm or less, and in order to obtain a magnesium compound having a better morphology, it is more advantageous that the water content is as small as possible, and generally 200 ppm or less is desirable.

The halogen in the reaction product of the above-mentioned metal magnesium, alcohol and halogen includes:
Bromine and iodine are preferable, and the form is not particularly limited. For example, the form may be dissolved in an alcohol solvent and used as a solution.

The amount of the alcohol to be used is not particularly limited, but is usually selected in the range of 2 to 100 mol, preferably 5 to 50 mol, per mol of metallic magnesium. If the amount of the alcohol is too large, it tends to be difficult to obtain a magnesium compound having a good morphology. On the other hand, if the amount is small, the reaction with the metallic magnesium may not proceed smoothly.

The halogen is usually present in an amount of at least 0.0001 g atom, preferably at least 0.0001 g atom, per mole of metallic magnesium.
It is used in a proportion of at least 05 g atoms, more preferably at least 0.001 g atoms. When the amount of the halogen used is less than 0.0001 g atom, when the obtained magnesium compound is used without being pulverized, the amount of titanium carried, the catalytic activity, the stereoregularity and the morphology of the produced polymer are reduced. Therefore, the pulverization of the obtained magnesium compound is indispensable, which is not preferable. The upper limit of the amount of halogen used is not particularly limited and may be appropriately selected within a range where a desired magnesium compound can be obtained, but is generally selected within a range of less than 0.06 g atom. The particle size of the obtained magnesium compound can be arbitrarily controlled by appropriately selecting the use amount of the halogen.

The reaction between the metal magnesium, the alcohol, and the halogen in the reaction product of the metal magnesium, the alcohol, and the halogen can be performed by a known method. For example, a desired magnesium compound can be obtained by reacting metal magnesium, an alcohol, and a halogen under reflux, usually for about 20 to 30 hours, until generation of hydrogen gas is no longer observed. Specifically, when iodine is used as the halogen,
A method in which solid iodine is charged into a mixture of metal magnesium and alcohol and then heated and refluxed, and a method in which an alcohol solution containing iodine is dropped into a mixture of metal magnesium and alcohol and then heated and refluxed ,
A method of dropping an alcohol solution containing iodine while heating a mixture of metallic magnesium and alcohol can be used.

In any method, it is preferable to carry out the reaction under an inert gas atmosphere such as a nitrogen gas or an argon gas, if necessary, using an inert organic solvent such as a saturated hydrocarbon such as n-hexane. . About the input of metal magnesium and alcohol, from the beginning,
It is not always necessary to put the whole amount into the reaction tank, and it may be divided and put. A particularly preferred form is a method in which the alcohol is charged in its entirety from the beginning, and the magnesium metal is divided and charged several times. This method
It is possible to prevent the temporary mass generation of generated hydrogen gas, it is extremely desirable from the viewpoint of safety, and it is possible to reduce the size of the reaction tank. Halogen droplets can be prevented from being entrained. The number of divisions may be determined in consideration of the scale of the reaction tank, and is not particularly limited, but is usually selected in the range of 5 to 10 in consideration of the complexity of the operation.

The reaction itself may be either a batch type or a continuous type. As a variant, a small amount of metallic magnesium is first charged into the alcohol which is initially charged in its entirety, and the product formed by the reaction is separated. It is also possible to repeat the operation of separating and removing the mixture into the above-mentioned tank and then adding a small amount of metallic magnesium again.

The reaction product thus obtained is
When used for the synthesis of the solid catalyst component as the component (A), a dried product thereof may be used, or a product obtained by filtration and washing with an inert solvent such as heptane may be used.
This magnesium compound can be used in the next step without performing purification, pulverization, or classification operation for adjusting the particle size.

In this case, the magnesium compound has a sphericity (S) represented by the following formula (1) of less than 1.60, and
It is preferable that the particle size distribution index (P) represented by the following formula (2) is less than 5.0.

That is, the sphericity (S) of the magnesium compound used as the component (a) is represented by the following equation (1).

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In the above equation (1), E1 represents the contour length of the projected particle, and E2 represents the circumference of a circle equal to the projected area of the particle.

Further, the particle size distribution index (P) of the magnesium compound used as the component (a) is represented by the following equation (2).

[0027]

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In the above formula (2), D90 is a particle diameter corresponding to a cumulative weight fraction of 90%. That is, it indicates that the weight sum of the particle group smaller than the particle diameter represented by D90 is 90% of the total weight of all the particles. D10 refers to a particle diameter corresponding to a cumulative weight fraction of 10%. In other words, it indicates that the weight sum of the particle group smaller than the particle diameter represented by D10 is 10% of the total weight of all the particles.

As described above, the magnesium compound used as the component (a) in the present invention according to claim 1 has a sphericity (S) represented by the above formula (1) of less than 1.60 and the above formula (2) It is preferable that the particle size distribution index (P) shown by the following is less than 5.0. Here, it is not preferable that the sphericity is 1.60 or more and the particle size distribution index is 5.0 or more, because the morphology of the produced polymer is poor and causes troubles in the process (for example, blockage of the polymer transfer line).

The magnesium compound having such sphericity and particle size distribution index is obtained by reacting less than 0.0001 g atom of halogen with 1 mol of metallic magnesium, alcohol and metallic magnesium. However, it shows good properties as a catalyst carrier material. As described above, the magnesium compound used as the component (a) in the present invention according to claim 1 is close to spherical, and has a sharp particle size distribution. It is preferable that the variation is very small.

Furthermore, in the present invention according to claim 1 ,
The magnesium compound used as the component (a) is Cu-K
In the X-ray diffraction spectrum measured with α rays, the scattering angle was 5
When three strong peaks appear in the range of ２０20 degrees, and these peaks are peak a, peak b, and peak c in order from the low scattering angle side, the peak intensity ratio b / c is
It is preferably 0.4 or more.

The magnesium compounds as described above may be used alone or in combination of two or more.

Next, as the titanium halide of the component (b), trivalent and tetravalent titanium halides can be used. In particular, the general formula (IV)

[0034]

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(Wherein R ⁹ is a hydrocarbon residue, X ¹ is a halogen atom, and m is a number of 0 to less than 4).

R ⁹ in the general formula (IV) is a hydrocarbon residue, which may be a saturated or unsaturated group, a linear or branched one, or a cyclic one. Or a compound having a hetero atom such as sulfur, nitrogen, oxygen, silicon, or phosphorus. Preferred examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group.

Specific examples of R ⁹ in the general formula (IV) include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, pentyl, hexyl Groups, heptyl, octyl, decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, phenethyl and the like.

X ¹ in the general formula (IV) is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. It is.

Representative examples of the titanium halide represented by the general formula (IV) include, for example, when m is 0,
When m is 1, for example, titanium tetrachloride, titanium tetrabromide, etc., ethoxytrichlorotitanium, n-propoxytrichlorotitanium, n-butoxytrichlorotitanium, etc.
Is 2, diethoxydichlorotitanium, di-n-
Examples of propoxytrichlorotitanium, di-n-butoxytrichlorotitanium, and when m is 3, include triethoxymonochlorotitanium, tri-n-propoxymonochlorotitanium, and tri-n-butoxymonochlorotitanium. One of these titanium halides may be used, or two or more of them may be used in combination.

Further, the electron-donating compound of the component (c) is an organic compound containing oxygen, nitrogen, phosphorus, or sulfur, and specific examples thereof include amines, amides, ketones, and nitriles. , Phosphines, phosphoramides, esters, ethers, thioethers, thioesters, acid anhydrides, acid halides, acid amides, aldehydes, organic acids, organosilane compounds having a Si-OC bond And the like.

More specifically, the electron-donating compound of the component (c) may be, for example, an organic acid such as aromatic carboxylic acid such as benzoic acid or p-oxybenzoic acid, succinic anhydride, benzoic anhydride. Acids, acid anhydrides such as p-toluic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, ketones having 3 to 15 carbon atoms such as benzoquinone, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde; Aldehydes having 2 to 15 carbon atoms such as naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, dichloromethyl Ethyl acetate, meta Methyl acrylic acid, ethyl crotonate,
Ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, toluyl Ethyl acrylate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, di-n-butyl phthalate, diisobutyl phthalate, diheptyl phthalate, 2 carbon atoms such as dicyclohexyl phthalate
To 18 esters, acetyl chloride, benzyl chloride, toluic acid chloride, anisic acid chloride and other acid halides having 2 to 15 carbon atoms, methyl ether, ethyl ether, isopropyl ether, t-butyl methyl ether, t-butyl ethyl Ethers having 2 to 20 carbon atoms such as ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, difel ether, ethylene glycol butyl ether, acetate amide,
Acid amides such as benzoic acid amide and toluic acid amide;
Amines such as tributylamine, N, N-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenedian; nitriles such as acetonitrile, benzonitrile and tolunitrile;
Examples include tetramethylurea, nitrobenzene, lithium butyrate, and the like.

As the electron donating compound of the component (c), monoesters and diesters of aromatic dicarboxylic acids are preferably used, and monoesters and diesters of phthalic acid are particularly preferable. Specific examples of the monoester and diester of the aromatic dicarboxylic acid include monomethyl phthalate, dimethyl phthalate, monomethyl terephthalate, dimethyl terephthalate, monoethyl phthalate, diethyl phthalate, monoethyl terephthalate, diethyl terephthalate, monopropyl phthalate, dipropyl phthalate, Monopropyl terephthalate, dipropyl terephthalate, monobutyl phthalate, dibutyl phthalate, monobutyl terephthalate,
Dibutyl terephthalate, monoisobutyl phthalate,
Examples thereof include diisobutyl phthalate, monoamyl phthalate, diamyl phthalate, monoisoamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl propyl phthalate. These electron donating compounds may be used alone or in combination of two or more.

When comparing the monoester and the diester of the aromatic dicarboxylic acid, which are preferable as the electron donating compound of the component (c), the diester is more preferable.
Further, among diesters of aromatic dicarboxylic acids, lower alkyl esters of phthalic acid having 1 to 5 carbon atoms are preferable, and dibutyl phthalate and diisobutyl phthalate are particularly preferable.

The solid catalyst component (A) of the present invention according to claim 1 comprises the above-mentioned components (a), (b) and (c) as essential components. )
Along with the components (a), (b) and (c), optionally
As the component (d), general formula (V)

[0045]

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(Wherein R ¹⁰ is a hydrocarbon residue, X ² is a halogen atom, and q is 0 or an integer of 1 to 3).

R ¹⁰ in the general formula (V) is a hydrocarbon residue, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group. And sulfur, nitrogen, oxygen, silicon,
It may have a hetero atom such as phosphorus. Preferred examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. Further, when the R ¹⁰ there are a plurality, to which may be the same or different from each other. Specific examples of the R ^10, can be mentioned those exemplified in the description of R ⁹ in the general formula (IV). X ² in the general formula (V) is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a chlorine atom and a bromine atom are preferable.
Particularly, a chlorine atom is preferred.

Specific examples of the silicon compound represented by the general formula (V) include, for example, 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 SiC
l ₂ , (C ₂ H ₅ O) ₃ Si Cl , C ₃ H ₇ OSiCl ₃ , (C ₃ H ₇ O) ₂ SiCl ₂ , (C ₃ H ₇
O) ₃ SiCl and the like. Among these, silicon tetrachloride (SiCl ₄ ) is particularly preferable. One of these silicon compounds may be used, or two or more thereof may be used in combination.

The silicon compound (d) optionally used is used in such a ratio that the molar ratio of the silicon compound / magnesium compound is usually in the range of 0.01 to 0.30, preferably 0.10 to 0.20. . If the molar ratio is less than 0.01, the effect of improving the catalytic activity and stereoregularity is not sufficiently exhibited, and the amount of fine powder in the produced polymer powder increases. Contains a lot of giant particles, which is not preferable.

The solid catalyst component (A) can be prepared by a known method (JP-A-53-43094, JP-A-55-13510).
No. 2, JP-A-55-135103, JP-A-5-135103
No. 6-18606).
For example, (1) a magnesium compound or a complex compound of a magnesium compound and an electron-donating compound is pulverized in the presence of an electron-donating compound and a pulverization aid used as desired, and reacted with a titanium halide. A method, (2) a method of reacting a liquid material of a magnesium compound having no reducing ability and a liquid titanium halide in the presence of an electron-donating compound to precipitate a solid titanium complex,
(3) a method in which a titanium halide is reacted with the compound obtained in the above (1) or (2), and (4) a method in which the compound obtained in the above (1) or (2) further comprises an electron donating compound and A method of reacting a titanium halide, (5) pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donating compound in the presence of an electron donating compound, a titanium compound, and a pulverization aid used as desired; After that, a method of treating with a halogen or a halogen compound, (6) above (1) to (4)
And a method of treating the compound obtained in the above with a halogen or a halogen compound.

Further, methods other than those described above include, for example, JP-A-56-166205 and JP-A-57-166205.
63309, JP-A-57-190004,
JP-A-57-300407, JP-A-58-470
The solid catalyst component (A) can also be prepared by the method described in JP-A-03-2003.

Also, oxides of elements belonging to groups II to IV of the periodic table, for example, oxides of silicon oxide, magnesium oxide, aluminum oxide and the like or oxides of elements belonging to groups II to IV of the periodic table are used. Including complex oxides, for example,
A solid obtained by supporting the magnesium compound on silica alumina or the like, an electron-donating compound, and a titanium halide in a solvent at 0 to 200 ° C, preferably 10 to 150 ° C.
By contacting at a temperature in the range of 2 minutes to 24 hours, a solid catalyst component can be prepared.

In the preparation of the solid catalyst component, an organic solvent inert to the above-mentioned magnesium compound, electron-donating compound and titanium halide is used as a solvent.
For example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, or mono- and polyhalogens of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms Halogenated hydrocarbons such as compounds can be used.

Next, the component (B) of the catalyst used in the method of the present invention according to claim 1 , that is, the organoaluminum compound is represented by the general formula (VI):

[0055]

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Wherein R ¹¹ is an alkyl group having 1 to 10 carbon atoms, X ³ is a halogen atom such as chlorine or bromine, and p is 1 to 3
Is the number of ) Can be used.

As such an aluminum compound,
For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dialkylaluminum monohalide such as dioctylaluminum monochloride And alkylaluminum sesquihalides such as ethylaluminum sesquichloride. One of these aluminum compounds may be used, or two or more thereof may be used in combination.

Further, in the method of the present invention according to claim 1, the component (C) of the catalyst has the general formula (II):

[0059]

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Wherein R ⁴ is a hydrocarbon residue in which the carbon atom adjacent to Si is a tertiary carbon atom, and R ⁵ is a straight-chain or branched-chain hydrocarbon residue. Organosilicon compounds are used.

In the organosilicon compound represented by the general formula (II), R ⁴ is a hydrocarbon residue in which the carbon atom adjacent to the Si atom is a tertiary carbon atom. The general formula (II)
R ⁵ in is a straight-chain or branched hydrocarbon residue, an aliphatic hydrocarbon group, especially a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms are preferred. Specific examples of such organosilicon compounds include, for example, dialkyldialkoxysilanes shown below.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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These dialkyldialkoxysilanes may be used alone or in combination of two or more.

The dial represented by the general formula (II)
By using kildialkoxysilane, high stereoscopic
Polymers with regularity and a wide molecular weight distribution can be obtained in high yield
can get.

Next, the method according to the second aspect of the present invention is used.
The catalyst to be used is described. The present invention according to claim 2
The catalyst used in the method, (A) (a) magnesium compound,
(b) contacting titanium tetrachloride with (c) an electron donating compound
The solid catalyst component obtained by
Product, and (C) an organosilicon compound represented by the general formula (III)
A catalyst consisting of a combination.

The catalyst in the method of the present invention according to claim 2
The component (A) of the above, ie, the solid catalyst component,
Compound, (b) titanium tetrachloride, and (c) an electron donating compound.
It is obtained by contacting an object. Claim 2
In the method of the present invention, the magnesium compound of the component (a)
As the object, for example, metallic magnesium, metallic magnesium
Alkyl obtained by reacting a compound with a halogenated hydrocarbon
Magnesium halide, dialkylmagnesium, halo
Magnesium Genide, or Magnesium Hydroxide, Oki
Magnesium chloride, dialkoxymagnesium, Al
Coxy magnesium halide, organic magnesium and
Magnesium obtained by reacting them with a halogenating agent
And the like.

Further, in the present invention according to claim 2,
Is a metal mag as the magnesium compound of the component (a).
Also preferred are the reaction products of nesium, alcohols and halogens.
It can be used properly. Metallic magnesium and alcohol
For the reaction product of Le and halogen, engaging in claim 1
As described in detail in the present invention. Also,
About sphericity, particle size distribution index, etc. of gnesium compounds
As described in detail in the present invention according to claim 1.
It is.

The magnesium compound as described above is for one kind
Or two or more of them may be used in combination.

Next, according to the second aspect of the present invention,
An electron-donating compound of component (c), which constitutes component (A) of the medium;
In some cases, together with component (a), component (b), and component (c)
(D) as a silicon compound that can be used for
Is the same as that described in the first aspect of the present invention.
Can be used.

The catalyst according to the second aspect of the present invention.
The component (A) is described in the present invention according to claim 1.
Can be prepared in the same manner as described above.

Next, in the method of the present invention according to claim 2,
(B) component of the catalyst used for
As the compound, the compound described in the present invention according to claim 1 is used.
The same one as described above can be used.

Further, in the present invention according to claim 2,
Is represented by the following general formula (III) as a component (C) of the catalyst.
Is used.

[0080]

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In the above general formula (III), R ⁶ is a branched hydrocarbon residue, R ⁷ is a cyclic saturated hydrocarbon residue,
R ⁸ represents a linear or branched hydrocarbon residue.

Specific examples of such a dialkyldialkoxysilane include, for example, isopropylcyclohexyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tert-butylcyclohexyldimethoxysilane, isopropylcyclohexyldiethoxysilane, isobutylcyclohexyldiethoxysilane, tert-butylcyclohexyl Diethoxysilane and the like can be mentioned.

The dial represented by the general formula (III)
By using kildialkoxysilane, high stereoscopic
Polymers with regularity and a wide molecular weight distribution can be obtained in high yield
can get.

With respect to the amount of each component of the catalyst used in the method of the present invention, first, the solid catalyst component of the component (A) is usually 0.00
An amount is used such that it is in the range from 05 to 1 mmol. The organoaluminum compound as the component (B) has an aluminum / titanium atomic ratio of usually 1 to 1,000, preferably 5 to 1000.
An amount is used such that it is in the range of 500. If this atomic ratio deviates from the above range, the catalytic activity becomes insufficient.

Further, the organosilicon compound as the component (C) has an organosilicon compound / titanium molar ratio of usually 0.1 to 500,
Preferably, an amount in the range from 1 to 100 is used. When the molar ratio is less than 0.1, the sustainability of the catalytic activity is poor, and the stereoregularity of the obtained polymer is insufficient. On the other hand, when it exceeds 500, the catalytic activity may decrease.

In the method of the present invention, (A)
An olefin homopolymer obtained by polymerizing at least one olefin in the presence of a catalyst system comprising a combination of a solid catalyst component as the component, an organoaluminum compound as the component (B), and an organosilicon compound as the component (C). Alternatively, a copolymer is produced.

As the olefin, for example, a compound represented by the general formula (VI)
I)

[0088]

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(Wherein R ¹² is a hydrogen atom or a group having 1 to 1 carbon atoms)
0 is a straight-chain or branched-chain hydrocarbon residue).

Specific examples of such α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1,
Examples include long-chain monoolefins such as decene-1, branched monoolefins such as 4-methylpentene-1, and vinylcyclohexane. These olefins may be used alone or in a combination of two or more.

Regarding the polymerization mode in the method of the present invention,
There is no particular limitation, for example, a slurry polymerization method using an inert hydrocarbon solution, a bulk polymerization method using no solvent, or a gas-phase polymerization method, and any method can be used.
Either a continuous polymerization method or a non-continuous polymerization method is possible. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

In a multi-stage polymerization reaction, for example, a two-stage polymerization reaction, the catalyst components (A), (B) and
In the presence of (C), for example, a polymerization reaction of propylene is carried out to produce a crystalline polypropylene, and then, in a second step, unreacted propylene subjected to the first-stage polymerization is removed or removed. Instead, a method of copolymerizing ethylene and propylene in the presence of the crystalline polypropylene and the catalyst can be used.

Further, regarding the reaction conditions in the process of the present invention, the olefin pressure is usually from normal pressure to kg / cm ² · G, and the reaction temperature is usually from 0 to 200 ° C., preferably from 5 to 200 ° C.
It is appropriately selected in the range of 0 to 100 ° C. The molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. further,
The reaction time depends on the type of the starting olefin and the reaction temperature and cannot be unconditionally determined, but is usually about 1 minute to 10 hours, preferably about 30 minutes to 5 hours.

[0094] As for the catalyst component, the component (A)
After the components (B) and (C) are mixed at a predetermined ratio and brought into contact with each other, an olefin may be immediately introduced to initiate polymerization, or about 0.2 to 3 hours after the contact. After aging, an olefin may be introduced. Further, this catalyst component can be supplied by suspending in an inert solvent, an olefin or the like.

In the present invention, post-treatment after polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after polymerization, the polymer powder derived from the polymerization vessel may be passed through a nitrogen gas stream or the like in order to remove olefins and the like contained therein, or if desired. If necessary, pelletization may be carried out from an extruder. At that time, a small amount of water, alcohol, or the like may be added to completely deactivate the catalyst. In the bulk polymerization method, after the polymerization, the monomer can be completely separated from the polymer led out of the polymerization vessel and then pelletized.

[0096]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The Mw / Mn measurement, sample preparation, and GPC measurement in the following Examples and Comparative Examples were performed by the following methods.

First, Mw / Mn was measured by the following method. (1) GPC (gel permeation chromatography) counts corresponding to the molecular weight M of polystyrene are measured using standard polystyrene of known molecular weight (monodisperse polystyrene, manufactured by Toyo Soda Co., Ltd.). Then, a calibration curve of the molecular weight M and the EV (Elution Volume) is created. (2) The gel permeation chromatogram of the measurement sample was measured by GPC, and the number average molecular weight Mn and the weight average molecular weight Mw were determined using the calibration curve prepared in (1) above.
Are calculated based on the following equations to determine Mw / Mn.

Number average molecular weight (Mn) = ΣMiNi / ΣNi Weight average molecular weight (Mw) = ΣMi ² Ni / ΣMiNi

Next, the preparation method of the sample is as follows. (A) The polymer was charged into an Ehrenmeyer flask together with the solvent o-dichlorobenzene, and 15 mg-polymer / 2 was added.
Prepare a solution with a concentration of 0 ml-solvent. (B) 0.1% by weight of 2,6-di-t-butyl-p-cresol is added as stabilizer to the polymer solution. (C) After being left at 140 ° C. for 1 hour, stirring is performed for 1 hour to completely dissolve the polymer and the stabilizer. (D) Next, the solution is filtered at a temperature of 135 to 140 ° C. using a 0.5 μm filter. (E) The filtrate is measured by GPC.

Further, the measurement conditions of GPC are as follows. (A) Apparatus: Model 1150C (manufactured by Water) (b) Column: TSKGMH-6, diameter 6 mm × 600 mm
(C) Sample volume: 400 µl (d) Temperature: 135 ° C (e) Flow rate: 1 ml / min

The following reagents were used in the following Examples and Comparative Examples. Ethanol: Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. Iodine: Wako Pure Chemical Industries, Ltd., reagent grade. Metallic magnesium: Granular (average particle size 350 μm).

The X-ray diffraction measurement was performed as follows. The magnesium compound was pulverized so as to have an average particle size of 10 μm. The pulverized product was vacuum-dried at room temperature, and the obtained dry powder was filled in a cell made of Mylar film under an inert gas atmosphere. The thickness of the Mylar film is 6 μm, and the thickness of the cell combining the Mylar film and the dry powder is 1 μm.
mm. This cell was attached to a powder X-ray diffractometer (manufactured by Rigaku Denki Kogyo KK), and the X-ray diffraction spectrum was measured by a transmission method. Copper (Cu) was used for the counter electrode, a voltage of 50 kV, a current of 120 mA, and a wavelength (λkα) of 1.543.
Angstrom conditions were used.

Further, the sphericity (s) was measured as follows. A sample of the dried magnesium compound (a) was subjected to a scanning electron microscope [JSM-25 manufactured by JEOL Ltd.].
SIII], an image was taken at an acceleration voltage of 5 kV and a magnification of 150 to obtain a negative. Next, the negative was subjected to image breaking processing by a transmission method. The image opening process is performed by an image opening device [Nexus 6
510 (2 MB)], 20 pixels (one pixel equals 1.389)
The following particles were cut, and the remaining particles were subjected to about 2,000 particles. The contour length E1 and the circumference E2 of a circle equal to the projected area of the particle were obtained by image analysis processing, and were calculated by the above equation (1).

Similarly, the particle size distribution index (p) is obtained by determining the particle size distribution of the particles through a sieve, plotting the distribution on a logarithmic distribution paper, and calculating the 90% particle size (D90) and the 10% particle size (D10). It was calculated by the above equation (2).

Example 1 (Claim 1) (1) Preparation of Solid Catalyst Component (A) A glass reactor (with an internal volume of about 6 liters) equipped with a stirrer was used.
Substitute sufficiently with nitrogen gas, ethanol about 2430 g,
16 g of iodine and 160 g of metallic magnesium were charged and stirred.
Under reflux conditions with stirring, no hydrogen gas was generated from within the system.
Until heated until the solid reaction product (ma
Gnesium compound). 500ml four-necked flask
Then, 60 ml of dehydrated n-heptane was synthesized by the above method.
Magnesium compound 16g, diethyl phthalate 2.3
After stirring at room temperature, 2.4 ml of silicon tetrachloride was added.
Then, the mixture was heated and reacted under reflux for 30 minutes. Then this
77 ml of titanium tetrachloride is added to the mixture, and the reaction is performed at 110 ° C. for 2 hours.
After washing, washing with n-heptane was carried out and
122 ml of titanium chloride was added and the reaction was carried out at 110 ° C. for 2 hours.
No, then by thorough washing with n-heptane
Thus, a fixed catalyst component (A) was obtained.

(2) Production of Olefin Polymer In a 1-liter stainless steel autoclave, n-
400 ml of butane, and then (B) component
2.0 mmol of triethylaluminum, as component (C)
0.25 mmol of di-t-butyldimethoxysilane and tita
0.005 mmole of the solid prepared in the above (1)
Charge the catalyst component (A), hydrogen pressure 0.5kg / cm ² · G, professional
2 hours at 70 ° C while maintaining the pyrene pressure at 7.0 kg / cm ² · G
During the polymerization, propylene was polymerized. As a result, the polypropylene
The yield of len is 660 kg / g of titanium,
Butane extraction residue (II) content is 98.3% by weight, intrinsic viscosity
[Η] was 1.48 dl / g. Also, calculated from high temperature GPC
The weight average molecular weight / number average molecular weight ratio (Mw / Mn) was 8.
Was 3.

Example 2 (Claim 2) (1) Preparation of solid catalyst component (A) Dehydrated n-heptane 6 was placed in a 500 ml four-necked flask.
0 ml, diethoxymagnesium 16 g, diethylphthale
After stirring at room temperature, 2.3 ml of silicon tetrachloride was added .
4 ml was added, the temperature was raised, and the mixture was reacted under reflux for 30 minutes. Next
Then, 77 ml of titanium tetrachloride was added thereto, and the mixture was heated at 110 ° C for 2 hours.
After the reaction, washing with n-heptane,
Further add 122 ml of titanium tetrachloride, and at 110 ° C for 2 hours
Perform the reaction and wash thoroughly with n-heptane.
Thus, a fixed catalyst component (A) was obtained. (2) Production of olefin polymer In a 1-liter stainless steel autoclave,
Put 400 ml of butane, 2.0 m of triethylaluminum
mol, tert-butylcyclohexyldimethoxysilane 0.
25 mmol and the solid catalyst component obtained in (1) above were
0.005 mmol, hydrogen pressure 0.5 kg / cm ² ,
Perform polymerization for 2 hours while maintaining pyrene pressure at 7.0 kg / cm ²
Was. Table 1 shows the results.

[0108] In Example 3 (claim 2) and Comparative Examples 1 to 3 Example 2, as the component (C), tert- Buchirushi
Polymerization was carried out in the same manner as in Example 2 except that silicon compounds shown in Table 1 were used instead of clohexyldimethoxysilane . The results are shown in Table 1.

Example 4 (Claim 2) (1) Preparation of solid catalyst component (A) Except that in Example 2 (1), a magnesium compound synthesized by the following method was used instead of diethoxymagnesium. Was carried out in the same manner as in Example 2 (1) to obtain a solid catalyst component. Glass reactor with stirrer (volume approx. 6
Liters) with nitrogen gas and ethanol about 2
430 g, iodine 16 g and metallic magnesium 160 g
Was added thereto, and the mixture was reacted under heating under reflux with stirring until hydrogen gas was no longer generated from the inside of the system to obtain a solid reaction product (magnesium compound).

[0110] The magnesium compound
When X-ray diffraction analysis was performed using Kα ray, 2θ = 5
Three diffraction peaks appeared in the range of ２０20 degrees. When these peaks were designated as peak a, peak b, and peak c in order from the low angle side, the peak intensity ratio b / c was 0.75. The sphericity (s) was 1.21 and the particle size distribution index (p) was 1.7.

(2) Production of olefin polymer Except for using the solid catalyst component (A) prepared in (1),
Polymerization was carried out in the same manner as in Example 2 . The results are shown in Table 1.

[0112]

[Table 1]

[0113]

According to the present invention, a combination of a solid catalyst component containing magnesium compound, titanium halide and an electron donating compound as an essential component, an organoaluminum compound, and a dialkyldialkoxysilane having a specific structure is used as a catalyst. By polymerizing the olefin used, it is possible to produce an olefin polymer having high stereoregularity, a wide molecular weight distribution, and good moldability in a high yield.

[Brief description of the drawings]

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

Continuation of the front page (72) Inventor Akinobu Sugawara 1-1, Anesaki Beach, Ichihara-shi, Chiba Prefecture Idemitsu Oil Chemicals Co., Ltd. (56) References JP-A-63-258907 (JP, A) JP-A-2-163104 ( JP, A) JP-A-3-33102 (JP, A) JP-A-2-229806 (JP, A) Patent 2624578 (JP, B2) Patent 2521836 (JP, B2) Patent 3039878 (JP, B2) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) (A) (a) metallic magnesium and alcohol
A magnesium compound which is a reaction product with a halogen ,
(b) a solid catalyst component containing titanium halide and (c) an electron donating compound as essential components, (B) an organoaluminum compound, and (C) a general formula (II) (Wherein, R ⁴ is a hydrocarbon residue in which the carbon atom adjacent to Si is a tertiary carbon atom, and R ⁵ is a linear or branched hydrocarbon residue.) A method for producing an olefin polymer, comprising contacting an olefin with a catalyst comprising a combination of a compound and polymerizing the olefin. 2. (A) (a) a magnesium compound, and (b) a tetrasalt
Titanium oxide and (c) an electron donating compound.
A solid catalyst component, and (B) an organoaluminum compound,
(C) General formula (III) (In the formula, R ⁶ is a branched hydrocarbon residue, R ⁷ is a cyclic saturated hydrocarbon residue, and R ⁸ is a straight or branched hydrocarbon residue.) A process for producing an olefin polymer, comprising contacting an olefin with a catalyst comprising the combination of Wherein the electron-donating compound in the solid catalyst component, The method according to claim 1 is at least one selected from among mono- and diesters of aromatic dicarboxylic acids. 4. The production method according to claim 2 , wherein the electron donating compound in the solid catalyst component is at least one selected from monoesters and diesters of aromatic dicarboxylic acids. 5. A magnesium compound in a solid catalyst component.
Object is the reaction between metallic magnesium, alcohol and halogen
The production method according to claim 2 or 4, which is a reaction product.