JP3039878B2 - 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 has excellent stereoregularity, excellent balance between rigidity and impact strength, good morphology, excellent film properties, and no odor problem. The present invention relates to a method for efficiently producing a high-quality olefin polymer using a highly active catalyst.

[0002]

2. Description of the Related Art Conventionally, an electron-donating compound and a silicon compound are added to a magnesium dialkoxide as a carrier,
Furthermore, a method is known in which a solid catalyst component obtained by reacting a titanium compound is polymerized with olefins using a Ziegler-Natta catalyst in which an organic aluminum compound and an electron donating compound are combined (Japanese Patent Laid-Open No. 1-149).
No. 806) and many other catalyst systems which are so-called Ziegler-Natta catalysts have been disclosed (Japanese Patent Publication No.
Nos. 52166, 60-25441, 59
And the like, and are used for polymerization of olefins. On the other hand, various techniques have been disclosed for the polymerization method, such as a prepolymerization method (Japanese Patent Publication No. 59-502).
No. 46, No. 57-45244, Japanese Unexamined Patent Publication No.
206407).

[0003] In these techniques, an electron donor is used for the purpose of improving stereoregularity at the time of preparing a solid catalyst component. However, unless a relatively large amount of an electron donor is added, the target is not used. Can not be reached. However, when a large amount of the electron donor is added, undesirable situations such as a decrease in catalytic activity and odor caused by the electron donor remaining in the polymer are caused.

In addition, prepolymerization is performed for the purpose of improving stereoregularity and improving the balance between impact strength and rigidity by improving stereoregularity. In this case, too, a large amount of prepolymerization must be performed. The purpose cannot be achieved. However, when the amount of pre-polymerization is increased, there arises a problem that deterioration of film characteristics due to generation of fish eyes or gel and deterioration of the surface of the injection molded product are unavoidable.

[0005]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the prior art, has a high stereoregularity, has a good balance between rigidity and impact strength, has a good morphology, and has a film. The object of the present invention is to provide a method for efficiently producing an olefin polymer having excellent quality using a highly active catalyst, such as having no problems such as deterioration of characteristics, surface deterioration of an injection molded product and odor. Things.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, by using a specific solid catalyst component, even if a small amount of an electron donor is added, the stereoregularity can be improved. A catalyst system that gives an olefin polymer having high reactivity is obtained, and since this catalyst system has a small amount of an electron donor, it has high activity and does not cause problems such as odor of the polymer. By using the system, an olefin polymer having a good morphology can be obtained even if the amount of prepolymerization is reduced, and since the amount of prepolymerization is small, when film-forming or injection-molding the olefin polymer, the film characteristics It has been found that there is no problem of deterioration or surface deterioration of the injection molded product, and the present invention has been completed based on this finding.

That is, the present invention relates to (A) a (a) magnesium compound and (b) at least one selected from monoesters and diesters of aromatic dicarboxylic acids, and (c) a compound represented by the general formula: TiX ¹ _n (OR ¹ A solid obtained by reacting a titanium compound represented by the formula: _4-n (I) (wherein X ¹ is a halogen atom, R ¹ is a hydrocarbon residue, and n is 0 or an integer of 1 to 4) When the olefin is polymerized in the presence of a catalyst comprising a catalyst component, (B) an organoaluminum compound and (C) an electron-donating compound, the following magnesium compounds are used: (1) metal magnesium, alcohol and 0 g per 1 g atom of magnesium; A reaction product of a halogen of 0.0001 g atoms or more, or (2) a metal magnesium, an alcohol and 0.1 g of magnesium per g atom.
A reaction product with a halogen of 0001 g atom or more, wherein S = (E1 / E2) ² (II) (E1 is a contour length of a projected particle, E2 is a circumference of a circle equal to a projected area of the particle) And the sphericity S is less than 1.60, and the formula P = D90 / D10 (III) (where D90 is a particle diameter corresponding to a cumulative weight fraction of 90%, and D10 is (The cumulative weight fraction is a particle size corresponding to 10%) having a particle size distribution index P of less than 5.0, and (A) less than 0.10 g of olefin reserve per 1 g of the solid catalyst component. An object of the present invention is to provide a method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of a polymerization product.

The solid catalyst component used as the component (A) of the catalyst in the method of the present invention comprises reacting (a) a magnesium compound with (b) a monoester or diester of an aromatic dicarboxylic acid with (c) a titanium compound. Is obtained by As the magnesium compound of the component (a),
A reaction product of metal magnesium, alcohol, and halogen is used. In this case, the magnesium compound of the component (a) has a sphericity S represented by the formula (II).
Is less than 1.60 and the particle size distribution index P represented by the formula (III) is less than 5.0.

The sphericity S represented by the above formula (II)
Is less than 1.60 and the particle size distribution index P represented by the formula (III) is less than 5.0, the magnesium compound as the component (a) is composed of metallic magnesium, alcohol and 1 g of metallic magnesium. Even if it is other than a reaction product with a halogen of 0.0001 g atom or more, it shows good properties as a carrier material for a catalyst.

Further, in the magnesium compound of the component (a), three strong peaks appear at a scattering angle of 5 to 20 ° in an X-ray diffraction spectrum measured by CuKα ray,
Moreover, these peaks are sequentially referred to as a peak a,
When peak b and peak c are set, the peak intensity ratio b /
Those having c of 0.4 or more are preferred.

When such a solid catalyst component is used as the component (A), a polymer powder having more improved catalytic activity, stereoregularity, and supported amount of titanium, and having better morphology can be obtained. The shape of the metal magnesium used at this time is not particularly limited, and any shape of the metal magnesium, for example, any of a granular shape, 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 is not particularly limited, but a lower alcohol having 1 to 6 carbon atoms is preferred, and ethanol is particularly preferred because it provides a solid catalyst component for improving the catalytic performance. The purity and water content of this alcohol are not particularly limited. However, when an alcohol having a high water content is used, magnesium hydroxide is formed on the surface of the metal magnesium, so that the water content is 1% by weight or less, especially 2000%.
It is preferable to use an alcohol of not more than ppm, and in order to obtain a magnesium compound having a better morphology, it is advantageous that the water content is as small as possible, but generally it is desirably 200 ppm or less. Further, as the halogen, bromine and iodine, particularly iodine are preferable, and the form thereof is not particularly limited. For example, the halogen may be dissolved in an alcohol solvent and used as a solution.

The amount of the alcohol used is usually 2 to 100 moles, preferably 5 to 5 moles, per mole of metallic magnesium.
It is selected in the range of 0 mol, but is not limited to this. If the amount of the alcohol is too large, it tends to be difficult to obtain a magnesium compound having a good morphology, and if the amount is too small, the reaction with the metallic magnesium may not proceed smoothly. Further, the halogen is usually 0.000 g / g atom of metallic magnesium.
It is used in a proportion of 1 g atom or more, preferably 0.0005 g atom or more, more preferably 0.001 g atom or more. 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,
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 as long as a desired magnesium compound can be obtained.
Selected within the range of less than an atom. Also, by appropriately selecting the amount of the halogen to be used, the particle size of the obtained magnesium compound can be arbitrarily controlled.

The reaction between the metal magnesium, the alcohol and the halogen can be carried out by a known method.
For example, metal magnesium, alcohol and halogen, until the generation of hydrogen gas under reflux is no longer observed
The desired magnesium compound can be obtained by carrying out the reaction usually in about 20 to 30 hours. Specifically, when iodine is used as the halogen, after charging solid iodine into a mixture of metal magnesium and alcohol, a method of heating and refluxing, iodine is contained in a mixture of metal magnesium and alcohol A method in which an alcohol solution is dropped and then heated and refluxed, a method in which an alcohol solution containing iodine is dropped while heating a mixture of metal magnesium and alcohol, and the like can be used. Further, 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 using an inert organic solvent such as a saturated hydrocarbon such as n-hexane in some cases. Regarding the charging of the metal magnesium and the alcohol, it is not always necessary to charge the entire amount to the reaction tank from the beginning, and they may be charged separately. 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 can prevent a temporary large amount 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, and it is possible to prevent entrainment of alcohol or halogen caused by temporary mass generation of hydrogen gas. The number of divisions may be determined in consideration of the scale of the reaction tank, and is not particularly limited. However, considering the complexity of the operation, it is usually selected in the range of 5 to 10 times.

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 into another. It is also possible to repeat the operation of separating and removing in a tank and then adding a small amount of metallic magnesium again.

When the reaction product thus obtained is used for producing the solid catalyst component (A), a dried product may be used, or after filtration, it may be filtered with an inert solvent such as heptane. You may use what was washed. This magnesium compound can be used in the next step without performing purification, pulverization, or a classification operation for adjusting the particle size.

The component (a) magnesium compound is nearly spherical and has a sharp particle size distribution. Further, even if each particle is taken, the variation in sphericity is extremely small. In this case, it is preferable that the sphericity S represented by the formula (II) is less than 1.60 and the particle size distribution index P represented by the formula (III) is less than 5.0. Here, D90 refers to a particle size corresponding to a cumulative weight fraction of 90%. That is, the weight sum of the particle group smaller than the particle diameter represented by D90 is 9% of the total weight of all the particles.
0%. D10 is the same.

Further, the magnesium compound obtained by using at least magnesium and alcohol as raw materials has a sphericity S represented by the above formula (II) of less than 1.60 and a particle size distribution represented by the above formula (III). Index P
Is less than 5.0, it can be suitably used as a catalyst carrier.

In the present invention, the magnesium compound (a) may be used alone or in combination of two or more. As the monoester or diester of the aromatic dicarboxylic acid as the component (b), a monoester or diester of phthalic acid is preferable. For example, monomethylphthalate, dimethylphthalate, monomethylterephthalate, dimethylterephthalate, monoethylphthalate, diethylphthalate, 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. Each of these may be used alone, or 2
A combination of more than one species may be used.

When the monoester and the diester of the aromatic dicarboxylic acid are compared, the diester is preferred. Further, among diesters of aromatic dicarboxylic acids, lower alkyl esters of phthalic acid having 1 to 5 carbon atoms are preferable, and dimethyl phthalate and diethyl phthalate are particularly preferable.

The titanium compound as the component (c) is represented by the general formula TiX ¹ _n (OR ¹ ) _4-n (I) (wherein X ¹ , R ¹ and n have the same meanings as described above). Is used. R ¹ in the general formula (I) is a hydrocarbon residue, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group. Or sulfur, nitrogen,
Although it may have a hetero atom such as oxygen, silicon, or phosphorus, a preferred hydrocarbon group is one having 1 carbon atom.
And 10 to 10 alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups and aralkyl groups. When a plurality of R ¹ are present, they may be the same or different. Specific examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, decyl, Examples include an allyl group, a butenyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a phenyl group, a tolyl group, a benzyl group, and a phenethyl group. X ¹ in the general formula (I) 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, and a chlorine atom is particularly preferable. Further, n is 0 or an integer of 1 to 4.

Examples of the titanium compound represented by the general formula (I) include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, Tetraalkoxytitanium such as tetracyclohexyloxytitanium and tetraphenoxytitanium; titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; methoxytitanium trichloride; ethoxytitanium trichloride; propoxytitanium trichloride; n -Alkoxytitanium halides such as butoxytitanium trichloride and ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium Monohalogenation such as dihalogenated dialkoxytitanium such as dichloride, di-n-propoxytitanium dichloride and diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride and tri-n-butoxytitanium chloride Trialkoxytitanium and the like can be mentioned, and among these, a high halogen-containing titanium compound, particularly titanium tetrachloride is preferable. These titanium compounds may be used alone or in combination of two or more.

In the present invention, in the preparation of the solid catalyst component (A), the above-mentioned components (a), (b) and (c), and optionally the component (d) may be used as a component of the general formula Si (OR ⁴ ) _{^{m X 2 4-m (IV}} ) (R 4 in the formula is a hydrocarbon residue, X ² is a halogen atom, m is 0 or 1 to 3 is an integer) it can be used a silicon compound represented by the.

R ⁴ in the general formula (IV) is a hydrocarbon residue, which may be a saturated group or an unsaturated group;
It may be linear, branched, or cyclic, and may have a heteroatom such as sulfur, nitrogen, oxygen, silicon, or phosphorus. Examples of the hydrogen 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. When a plurality of R ⁴ are present, they may be the same or different. Specific examples of R ⁴ include those exemplified in the description of R ¹ in the general formula (I). X ² in the general formula (IV) 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, and a chlorine atom is particularly preferable.

Specific examples of such a silicon compound include SiCl ₄ , CH ₃ OSiCl ₃ , (CH ₃ O) ₂ Si
Cl ₂ , (CH ₃ O) SiCl, C ₂ H ₅ OSiCl ₃ ,
(C ₂ H ₅ O) ₂ SiCl ₂ , (C ₂ H ₅ O) ₃ SiCl, 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 which 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 of component (d) optionally used has a molar ratio of silicon compound / magnesium compound of usually 0.01 to 0.30, preferably 0.1 to 0.30.
It is used in such a ratio as to be in the range of 0 to 0.20. When 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 preparation of the solid catalyst component (A) in the present invention is preferably carried out as follows. That is,
A magnesium compound as the component (a), a monoester or diester of an aromatic dicarboxylic acid as the component (b), a titanium compound as the component (c), and a silicon compound as the component (d) used as desired are mixed with an inert solvent. Inside, a contact reaction is caused by stirring at a predetermined temperature for a predetermined time.

In this case, the amount of the monoester or diester of the aromatic dicarboxylic acid used is usually selected within the range of less than 0.1 mol per 1 g of magnesium in the magnesium compound of the component (a). If the amount exceeds 0.1 mol, the resulting polymer has a strong odor, and the deodorizing step becomes indispensable, and the catalyst activity tends to decrease. The order of addition of the components is not particularly limited, and the components may be added simultaneously or sequentially.

The solvent may be any solvent as long as it is inert, for example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and saturated or unsaturated ones having 1 to 12 carbon atoms. And halogenated hydrocarbons such as mono- and polyhalogen compounds of aliphatic, alicyclic and aromatic hydrocarbons. The reaction using these solvents is a preferred embodiment of the present invention, but can be carried out without a solvent. In this case, for example, the components may be directly mechanically mixed and reacted by a ball mill or the like. The temperature of the reaction is usually
It is effective to set the temperature to -10 to 150C, preferably 20 to 120C, and the polymerization activity of the obtained catalyst is increased.
The reaction time depends on the reaction temperature, and may be appropriately selected according to the reaction temperature.

Next, the solid substance thus obtained is washed with a solvent, and then a titanium compound is again charged and reacted.
In this reaction, the reaction temperature is usually 20 to 200
° C, preferably in the range of 50 to 150 ° C, and the reaction time is generally selected in the range of 5 minutes to 10 hours, preferably 30 minutes to 5 hours. The desired solid catalyst component (A) is obtained by washing the solid product obtained by this reaction with an inert hydrocarbon such as pentane, hexane, cyclohexane or n-heptane, if necessary. As for the composition of the solid catalyst component (A) thus prepared, the magnesium / titanium atomic ratio is usually 2 to 2.
100, the halogen / titanium atomic ratio is in the range of 5-100.

The aluminum compound used as the component (B) of the catalyst in the present invention includes, for example, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, and diisopropylaluminum. Examples include dialkylaluminum monohalides such as aluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride. Of these, lower alkyl having 1 to 5 carbon atoms Trialkyl aluminum having a group is preferred, especially trimethyl aluminum,
Triethylaluminum, tripropylaluminum, tributylaluminum and the like are preferred. These aluminum compounds may be used alone or in combination of two or more.

The electron-donating compound used as the component (C) in the catalyst of the present invention is an organic compound containing oxygen, nitrogen, phosphorus, or sulfur. Specific examples thereof include amines, amides, and the like. Ketones, nitriles, phosphines, phosphoramides, esters,
Examples include ethers, thioethers, thioesters, acid anhydrides, acid halides, acid amides, aldehydes, organic acids, and organic silane compounds having a Si—O—C bond.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid: acid anhydrides such as succinic anhydride, benzoic anhydride and p-toluic anhydride: acetone; C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone: C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde: methyl formate , Methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate,
Ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid Butyl, octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, methyl toluate, ethyl toluate, 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, di-isobutyl phthalate, phthalic acid C2 to C18 esters such as diheptyl and dicyclohexyl phthalate: C2 to C15 acid halides such as acetyl chloride, benzyl chloride, toluic acid chloride and anisic acid chloride: methyl ether, ethyl ether, isopropyl ether, Ethers having 2 to 20 carbon atoms such as t-butyl methyl ether, t-butyl ethyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether: acetate amide, benzoic acid amide, Acid amides such as toluic acid amide: tributylamine, N, N-dimethylpiperazine,
Tribenzylamine, aniline, pyridine, picoline,
Examples thereof include amines such as tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, and trinitrile, tetramethylurea, nitrobenzene, and lithium butyrate.

Examples of the organosilicon compound having a Si—O—C bond include, for example, alkoxysilane and aryloxysilane. An example of this is
General formula R ⁵ _p Si (OR ⁶ ) _4-p (V) (wherein R ⁵ is an alkyl group, cycloalkyl group, aryl group, alkenyl group, haloalkyl group, aminoalkyl group or halogen atom, and R ⁶ is alkyl Group, cycloalkyl group, aryl group, alkenyl group or alkoxyalkyl group, p is 0 or an integer of 1 to 3, and when there are a plurality of R ⁵ , they may be the same or different. When there are a plurality of R ^{6 s} , they may be the same or different).

Other examples include siloxanes having an OR ⁶ group or silyl esters of carboxylic acids. Further, as another example, a silicon compound having no Si—O—C bond and an organosilicon compound having an OC bond may be preliminarily reacted or may be reacted during the polymerization of α-olefin to obtain Si—O—C Examples thereof include those converted into an organosilicon compound having a bond. For example, a combination of SiCl ₄ and an alcohol can be considered.

Specific examples of the organosilicon compound having a Si—O—C bond include trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, γ-
Chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, Vinyl tributoxy silane, ethyl silicate, butyl silicate, trimethylphenoxy silane, methyl triaryloxy silane, vinyl tris (β-methoxyethoxy) silane, vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane, and the like.

Among the above various electron donating compounds, preferred are esters, ethers, ketones, acid anhydrides, and organic silane compounds having a Si--O--C bond.

In particular, phthalic acid esters such as di-n-butyl phthalate, di-isobutyl phthalate, diheptyl phthalate and dicyclohexyl phthalate may be used in combination with ethers such as t-butyl methyl ether and t-butyl ethyl ether. And alkyl esters of aromatic carboxylic acids, for example, having 1 carbon atom of an aromatic carboxylic acid such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid.
Preferred are alkyl esters (4) to (4), trialkoxysilane, etc., and also preferred are aromatic ketones such as benzoquinone, aromatic carboxylic anhydrides such as benzoic anhydride, and ethers such as ethylene glycol butyl ether.

Regarding the amount of each component of the catalyst used in the method of the present invention, the organoaluminum compound of the component (B)
An amount is used such that the aluminum / titanium atomic ratio is usually in the range of 1 to 1000, preferably 10 to 500. If this atomic ratio deviates from the above range, the catalytic activity becomes insufficient. Further, the electron-donating compound (C) is used in such an amount that the molar ratio of the electron-donating compound / organoaluminum compound is usually in the range of 0.05 to 0.5. If the molar ratio is less than 0.05, the stereoregularity of the obtained polymer is insufficient, and if it exceeds 0.5, the catalytic activity decreases.

The olefin used in the method of the present invention is represented by the general formula R ⁷ —CH ＝ CH ₂ (VI) (wherein R ⁷ is a hydrogen atom or a linear or branched carbon atom having 1 to 10 carbon atoms). Which is a hydrogen residue)
Olefins are preferably used. Specifically, long-chain monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1, and branching of 4-methylpentene-1 Monoolefins, vinylcyclohexane and the like can be mentioned. These olefins may be used alone or in combination of two or more.

Among the olefins, ethylene and propylene are particularly preferred. In the present invention, dienes such as butadiene and other various olefins can also be used.

In the method of the present invention, first, (A)
An olefin is prepolymerized in the presence of a catalyst in which a solid catalyst component, (B) an organoaluminum compound and (C) an electron donating compound are mixed at a predetermined ratio. At this time, the amount of the prepolymerized product needs to be less than 0.10 g per 1 g of the solid catalyst component (A). When the amount is 0.10 g or more, when a film is molded from the obtained polymer, the film characteristics are remarkably reduced, such as occurrence of gel fish eyes and a decrease in haze value, and also in the case of injection molding. Tend to have poor surface characteristics.

The reaction temperature in this prepolymerization is usually 5
It is selected in the range of 5-75 ° C. The olefin pressure is
Usually, the pressure is selected from the range of normal pressure to 50 kg / cm ² · G, but conditions are appropriately selected so that the amount of the prepolymerized product falls within the above-mentioned range.

Next, after preliminarily polymerizing in this way,
The olefin is fully polymerized in the presence of the catalyst and the prepolymerized product. There is no particular limitation on the polymerization mode in this main polymerization, and any system such as a slurry polymerization method using an inert hydrocarbon solvent, a bulk polymerization method using no solvent, or a gas phase polymerization method can be used. Either a continuous polymerization method or a discontinuous polymerization method is possible. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

Further, the reaction conditions are appropriately selected in such a manner that the olefin pressure is usually from normal pressure to 50 kg / cm ² · G, and the reaction temperature is usually from 0 to 200 ° C., preferably from 30 to 100. The molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. The reaction time depends on the type of the olefin as the raw material and the reaction temperature and cannot be unconditionally determined, but is usually about 5 minutes to 10 hours, preferably about 30 minutes to 5 hours.

As for the catalyst component in the present invention, the component (A), the component (B) and the component (C) are mixed at a predetermined ratio and brought into contact with each other. It may be carried out, or after aging for about 0.2 to 3 hours after the contact, olefin may be introduced to perform prepolymerization. Further, this catalyst component can be supplied by suspending in an inert solvent, an olefin or the like.

In the present invention, the post-treatment after the 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,
In order to remove olefins and the like contained therein, it may be passed through a nitrogen gas stream or the like, or may be pelletized by an extruder, if desired, in order to completely deactivate the catalyst. , A small amount of water, alcohol and the like can also be added. 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. next,
One example of an embodiment of the present invention is shown in a flowchart in FIG. 1 of the accompanying drawings.

[0048]

According to the present invention, by using a specific solid catalyst component, a catalyst system which gives an olefin polymer having high stereoregularity can be obtained even with the addition of a small amount of an electron donor. Since the addition amount of the electron donor is small, it has high activity and does not cause the problem of odor of the polymer. In addition, by using this catalyst system, an olefin polymer having a good morphology can be obtained even if the amount of prepolymerization is reduced, and the amount of prepolymerization is small. In addition to obtaining a film having good film properties free of generation of gel or gel, when injection molding is performed, there is no problem of surface deterioration of a molded product.

[0049]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples, the following reagents were used.

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). Further, 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. Mylar film thickness is 6μm
The thickness of the cell combined with the mylar film and the dry powder was 1 mm. This cell was attached to a powder X-ray diffractometer [manufactured by Rigaku Denki Kogyo Co., Ltd.]
The line diffraction spectrum was measured. Copper (Cu) for the counter electrode
Using a voltage of 50 kV, a current of 120 mA, and a wavelength (λk
α) The condition of 1.543 Å was used.

The sphericity S was measured as follows. A sample of the magnesium compound after drying (a)
Scanning electron microscope [JSM-25S, manufactured by JEOL Ltd.
III], projecting at an acceleration voltage of 50 kV and 150 times,
I got a negative. Next, the negative was subjected to image analysis processing by a transmission method. In the image analysis processing, particles of 20 pixels or less (one pixel is 1.389 μ × 1.389 μ) or less are cut by an image analysis device [manufactured by Nexus Corp., 6510 (2 MB)], and about 2,000 remaining particles are cut. went. By the image analysis processing, the contour length E1 and the circumference E2 of the circle equal to the projected area of the particle were obtained, and were calculated by the formula (II).
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,
The particle diameter D90 and the 10% particle diameter D10 were determined and the (I)
II) It was calculated by the equation.

Example 1 (1) Preparation of Magnesium Compound A glass container equipped with a stirrer having an internal volume of about 6 liters was sufficiently replaced with nitrogen gas, and then ethanol about 2430 was added thereto.
g, 16 g of iodine and 160 g of metallic magnesium were added thereto, and the mixture was stirred and reacted under reflux conditions until no hydrogen gas was generated from the system to obtain a reaction product. The solid product was subjected to X-ray diffraction analysis using CuKα radiation. As a result, three diffraction peaks appeared in the range of 20 = 5 to 20 °. When these peaks were designated as peak a, peak b, and peak c in order from the lower angle side, the peak intensity ratio b / c was 0.75. The sphericity S is 1.2
1, the particle size distribution index P was 1.7.

(2) Preparation of solid catalyst component (A) In a 500 ml glass three-necked flask sufficiently purged with nitrogen gas, 16 g of the magnesium compound (not pulverized) obtained in the above (1) was placed. , Purified heptane 80m
1, 2.4 ml of silicon tetrachloride and diethyl phthalate
0 ml was added. While maintaining the inside of the system at 90 ° C and stirring, 77 ml of titanium tetrachloride was added and reacted at 110 ° C for 2 hours. Then, a solid reactant was separated and washed with purified heptane at 80 ° C. Furthermore, titanium tetrachloride 122m
was added and reacted at 110 ° C. for 2 hours, and then sufficiently washed with purified heptane to obtain a solid catalyst component (A).

(3) Preliminary polymerization The solid catalyst component (A) obtained in the above (2) was converted into a 1 l heptane slurry, placed in a stainless steel autoclave having an internal volume of about 10 l, and triethyl aluminum 20 mm
ol, 15 mmol of diphenyldimethoxysilane, and propylene to 0.4 kg / cm ² · G.
Prepolymerization was performed at 0 ° C. for 10 minutes. Thereafter, the plate was washed three times with 1 l of n-heptane. Table 1 shows the amount of this prepolymerization.

(4) Polymerization of Propylene 4 l of purified heptane was added to the prepolymer obtained in (3).
15 mmol of triethylaluminum, 1.5 mmol of diphenyldimethoxysilane and the solid catalyst component (A) (0.05 mmol in terms of titanium atom) were added, hydrogen was added up to 1.5 kg / cm ² · G, and the total pressure was 8 k.
Polymerization of propylene was performed at 70 ° C. for 2 hours at g / cm ² · G. Table 1 shows the results. In addition, the stereoregularity and fish eye in Table 1 mean the following.

Stereoregularity The stereoregularity is represented by the insoluble content after 6 hours of extraction with boiling heptane.・ Fish Eye After adding antioxidant to powdery polymer and granulating,
Thickness 3 formed using a film forming machine with a screw diameter of 20 mm
The 0 μm film is represented by the number of fish eyes having a diameter of 0.2 mm or more measured by a defect detection device (manufactured by Takenaka System Equipment).

Example 2 Example 2 was carried out in the same manner as in Example 1 except that the amount of iodine in the preparation of the magnesium compound (1) was changed to 11.2 g. Table 1 shows the results. In this case, the peak intensity ratio b / c is 0.73, and the sphericity S is 1.
22, the particle size distribution index P was 1.7.

Example 3 Example 3 was carried out in the same manner as in Example 1 except that the polymerization time in the preliminary polymerization of (3) was changed to 5 minutes. Table 1 shows the results.

Example 4 In the preparation of the solid catalyst component (A) of (2) in Example 1, instead of using 2.0 ml of diethyl phthalate,
Example 1 was repeated except that 1.8 ml of dimethyl phthalate was used.
It carried out similarly to. Table 1 shows the results.

Example 5 In the polymerization of propylene of (4) in Example 1,
The amount of triethylaluminum used was changed from 15 mmol to 2
It carried out similarly to Example 1 except having changed to 0 mmol. Table 1 shows the results.

Example 6 Example 6 was carried out in the same manner as in Example 1 except that the amount of diethyl phthalate used was changed to 4.0 ml in the preparation of the solid catalyst component (A) of (2). Table 1 shows the results.

Comparative Example 1 (1) Magnesium Compound A commercially available magnesium diethoxide pulverized with a ball mill so that the average particle diameter becomes 25 μm was used. The following steps (2), (3) and (4) were performed in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 The procedure of Example 1 was repeated, except that the polymerization time in the preliminary polymerization of (3) was changed to 40 minutes. Table 1 shows the results.

Comparative Example 3 The procedure of Example 1 was repeated, except that no iodine was used in the preparation of the magnesium compound (1). At this time, the sphericity S of the magnesium compound was 1.87, and the particle size distribution index P was 7.6. Other results are shown in Table 1.

[Table 1]

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of an embodiment of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-27309 (JP, A) JP-A-63-165408 (JP, A) JP-A-63-223008 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (4)

(57) [Claims] (A) a (a) magnesium compound and (b) at least one selected from monoesters and diesters of aromatic dicarboxylic acids, and (c) a general formula TiX ¹ _n (OR ¹ ) _{4- n} (wherein X ¹ is a halogen atom, R ¹ is a hydrocarbon residue, and n is an integer of 0 or 1 to 4), and a solid catalyst component obtained by reacting with a titanium compound represented by the formula (B): When polymerizing an olefin in the presence of a catalyst comprising an organoaluminum compound and an electron donating compound (C), the magnesium compound is formed by reaction of metallic magnesium with an alcohol and a halogen of 0.0001 g atom or more per g atom of magnesium. Wherein the olefin is polymerized in the presence of less than 0.10 g of an olefin prepolymerization product per 1 g of the solid catalyst component (A). A method for producing a fin polymer. 2. (A) (a) a magnesium compound and (b) at least one selected from monoesters and diesters of aromatic dicarboxylic acids, and (c) a general formula TiX ¹ _n (OR ¹ ) _{4- n} (wherein X ¹ is a halogen atom, R ¹ is a hydrocarbon residue, and n is an integer of 0 or 1 to 4), and a solid catalyst component obtained by reacting with a titanium compound represented by the formula (B): In polymerizing an olefin in the presence of a catalyst comprising an organoaluminum compound and an electron-donating compound (C), the magnesium compound is reacted with metallic magnesium, an alcohol and a halogen of 0.0001 g atom or more per g atom of magnesium. a product, the formula ^{S = (E1 / E2) 2} ( contour length of the projection of the E1 particles in the formula, E2 is the circumferential length of a circle equal to the projected area of the grain) sphericity S represented by Less than 1.60 and the formula P = D90 / D10 (D90 in the formula is a particle size corresponding to a cumulative weight fraction of 90%, and D10 is a particle size corresponding to a cumulative weight fraction of 10%. ) Is used, and the olefin is polymerized in the presence of an olefin prepolymerization product of less than 0.10 g per 1 g of the solid catalyst component (A). A method for producing an olefin polymer. 3. The method according to claim 1, wherein the halogen is iodine.
The method for producing the olefin polymer according to the above. 4. In the preparation of the solid catalyst component (A), the amount of the component (b) charged is from 0.
4. The process for producing an olefin polymer according to claim 1, wherein the amount is less than 1 mol.