JPS59122505A - Catalyst component for polymerization of olefin - Google Patents

Abstract

PURPOSE:To provide the titled catalyst component having high activity and excellent effect for the molecular weight control with hydrogen, and capable of giving a polymer having high bulk density, by contacting an Mg alkoxide with an Mg halide, and contacting the product with a halogenated hydrocarbon, etc. CONSTITUTION:The objective catalyst component is prepared by contacting (A) a material obtained by contacting a magnesium alkoxide (preferably the one thermally dried and pulverized under reduced pressure) with a magnesium halide (preferably MgCl2), with (B) a halogenated hydrocarbon (e.g. methyl chloride), (C) an electron donor (preferably an alkyl benzoate, etc.) and (D) a titanium compound (preferably titanium tetrachloride). The catalyst component is usually combined with an organic Al compound and used for the (co)polymerization of an olefin. EFFECT:It increases the melt index of resultant polymer. The catalytic activity can be kept to the original level even under high partial pressure of hydrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a catalyst component for olefin polymerization, and more particularly, the present invention relates to a catalyst component for olefin polymerization, and more particularly, the present invention relates to a catalyst component for olefin polymerization, and more particularly, an olefin@polymer or copolymer having a high bulk density. The present invention relates to a catalyst component that can be produced at a high rate.

BACKGROUND TECHNOLOGY Conventionally, olefins, such as ethylene, have been polymerized α
- Catalyst components containing titanium compounds are widely known as copolymerization catalysts with olefins. In order to increase the activity of this catalyst or increase the catalytic efficiency per titanium in the catalyst component, several attempts have been made to bring a titanium compound into contact with a metal compound that has undergone various treatments, such as a magnesium compound. There is.

For example, a method in which a magnesium oxygen-containing compound is reacted with a 710 genating agent and then brought into contact with a titanium halide (Japanese Unexamined Patent Publication No. 1985-8595), a method in which a magnesium compound containing a hydroxyl group and a magnesium alkoxide are co-pulverized; , method of contacting titanium halide (
Japanese Patent Publication No. 46-54098), method of co-pulverizing magnesium halide, magnesium alkoxide, and titanium halide (Japanese Patent Application Laid-Open No. 80585/1985), after co-pulverizing magnesium halide and titanium compound, tetrahalogen A method of reacting with titanium chloride (Japanese Unexamined Patent Publication No. 55-1-510'+4) is known.

However, although the polymerization catalysts using the catalyst components obtained by these methods have improved catalytic activity, 1) the bulk density of the obtained polymer is low, the productivity of the polymerization equipment is reduced, and 2) the polymerization takes a long time. In the case of time, the activity of the catalyst decreases rapidly, ■
When hydrogen is used as a molecular weight regulator, the effect of controlling the molecular weight is small. Therefore, in order to increase the melt index of the polymer, a high hydrogen partial pressure or a high polymerization temperature is required.
The reactivity with other olefins as a commoner in copolymerization is low, and therefore a high como/mer boiling point is required. Problems remain, such as the bulk density of the copolymer decreases and a large amount of solvent-soluble low molecular weight polymer is produced, making it impossible to produce a copolymer at a high yield.

DISCLOSURE OF THE INVENTION OBJECTS OF THE INVENTION The present inventors have solved the problems mentioned above, particularly olefin copolymers,
For example, as a result of intensive studies to solve the problems in producing copolymers of ethylene and α-olefin, we found that contact products of magnesium alkoxide and magnesium halides, halogenated hydrocarbons, electron-donating compounds, and When a solid component obtained by contacting a titanium compound or a solid component obtained by contacting the solid component with an organoaluminum compound is used as a catalyst component together with an organoaluminum compound, olefin polymerization and olefin and other The present invention was completed by discovering that copolymerization with olefins proceeds effectively.

SUMMARY OF THE INVENTION The present invention provides (1) a catalyst component for olefin polymerization obtained by contacting a contact product of a magnesium alkoxide with a magnesium halide, a halogenated hydrocarbon, an electron donating compound, and a titanium compound, and (2) a magnesium alkoxide. The subject matter is a catalyst component for olefin polymerization obtained by contacting an organic aluminum compound with a solid component obtained by contacting a contact product with a magnesium halide, a halogenated hydrocarbon, an electron-donating compound, and a titanium compound. .

Each raw material used in preparing the catalyst component in the present invention will be explained.

(1) Magnesium alkoxide The magnesium alkoxide used in the present invention is represented by the general formula Mg (ORl (OR'l). In the formula, R and R1 have 1 to 20 carbon atoms, preferably 1 to 10 These are alkyl, alkenyl, cycloargyl, aryl, and aralkyl groups. The parent group, R, and R1 may be the same or different.

Examples of these compounds include “g (OCH3)2, V
Lg(OC2F(512, Vig(OCH3J(0(4)
F(51,Mg(01-C3H712,Mg(OCsH
y12. lv(g, tOc4H, 12, tJg(Ol
-C4H0+2,Mg (OC4Hg l (,01-
C4Hg 1, vig (Oca Hg l (○5e
c-C,Hgl,Vro(OCIIH13't%"
g(oc8H,,l, ,Mg(OC6Ho 12
1v,g('0CaHs 12,Mg(OC6E(4C
H312, Mg(OCH, C, FI5).

etc. can be mentioned.

When these magnesium alkoxides are used, it is desirable to dry them, and it is particularly desirable to dry them by heating under reduced pressure. Furthermore, it is preferable to use one that has been dried and then ground.

Examples of magnesium halides include magnesium cybaride, magnesium chloride, magnesium bromide,
Magnesium iodide is preferred, especially magnesium chloride.

For convenience of use, it is usually advantageous to use powdered magnesium halides with an average particle size of about 1 to 50 μm, but those with even larger particle sizes can also be used.

Preferably, these magnesium halides are so-called anhydrous ones that do not substantially contain water of crystallization. Therefore, when using a commercially available product, it should be heated at 200 to 60°C* or under reduced pressure in the presence of an inert gas such as nitrogen before use.
It is preferable to heat the treatment at a temperature of 00 to 400°C, but the temperature is not particularly limited.

(3) Halogenated hydrocarbon The halogenated hydrocarbon used in the present invention has 1 to 1 carbon atoms.
Mono- and dihalogen substituted products of two saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons. Specific examples of these compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon iodide, ethyl chloride,
Ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1゜2-dibromoethane, 1,2-short ethane, methylchloroform, methylbromoform,
Methyl iodoform, 1,1,2-trichloroethylene, 1. i, 2-tribromoethylene, 1.1.2.
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffinic compounds include chlorocyclopropane, tetrachlorocyclopenkune, hexachloropentadiene, and hexachlorocyclohexane; aromatic compounds include chlorobenzene, bromobenzene, ○-dichlorobenzene, and p-dichlorobenzene. , hexachlorobenzene, hexabromobenzene, pencitrichloride, p-chloropencitrichloride, and the like.

Not only one kind but also two or more kinds of these compounds may be used.

Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichlorethoxytitanium, trichlorobutoxytitanium, dichlorjetoxytitanium, and dichlorodibutoxytitanium. , dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride, and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

The electron-donating compounds used in the present invention include carboxylic acids, carboxylic esters, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, organic groups and carbon atoms. phosphorus, arsenic and antimony compounds, bound through oxygen
Preferred among these are phosphoamides, thioethers, thioesters, and carbonate esters,
Those used include carboxylic acid esters, alcohols, and ethers.

Specific examples of carboxylic acid esters include butyl formate, ethyl acetate, butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl isobutyrate, methyl methacrylate, diethyl maleate, diethyl tartrate, ethyl dichloroxanecarboxylate, and ethyl benzoate. , ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl p-tertiary butylbenzoate, dibutyl phthalate, diallyl phthalate, α
Examples include, but are not limited to, -ethyl naphthoate. Among these, alkyl esters of aromatic carboxylic acids, particularly alkyl esters of benzoic acid or nuclear substituted benzoic acids having 1 to 8 carbon atoms such as p-methylbenzoic acid and p-methoxybenzoic acid, are preferably used. Alcohols are represented by the general formula ROH. In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms. Specific examples include Iri, methyl, ethanol, propyl
-ol, isopropanol, but/ol, isobut/ol, pentanol, hexanol, octatool, 2-ethylhexanol, cyclohexynol, benzyl alcohol, allyl alcohol, and the like. Ethers are represented by the general formula ROR. In the formula, R and R' are alkyl, alkenyl, cycloalkyl, having 1 to 12 carbon atoms,
They are aryl and aralkyl, and R and R1 may be the same or different. Cyclic ethers can also be used.

Atypical examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, ';-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and tetrahydrofuran. , 1.
4-dioxane, etc.

(6) Organoaluminum compound The organoaluminum compound has the general formula RnAtx3-n
(However, R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and D is 1≦M
<Title by any number within the range of 5. ), preferably having 1 to 18 carbon atoms, such as trialkylaluminium, dialkylaluminum heptivalide, monoalkylaluminum civalide, alkyl aluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride. Particularly preferred is an alkylaluminum compound having 2 to 6 carbon atoms, a mixture thereof, or a complex compound. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylaluminum chloride, etc. Monoalkylaluminum cybarides such as dialkylaluminum monohalide, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, dimethylaluminum methoxide, Dialkyl aluminum monoalkoxides such as diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropylaluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride Dialkyl aluminum hydrides such as

Among these, dialkylaluminum monohalides, particularly diethylaluminum chloride, are preferred.

These dialkylaluminum monohalides may be combined with other organoaluminum compounds such as triethylaluminum, triisobutylaluminum, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, which are industrially easy to handle, or their combinations. It can be used in combination with a mixture or a complex compound.

The catalyst component of the present invention can be obtained by contacting a contact product of magnesium alkoxide with a magnesium halide (hereinafter referred to as the contact product), a halogenated hydrocarbon, a sleep donor compound, and a titanide a. These are the obtained solid component I and the solid component (2) obtained by further contacting this solid component I with an organoaluminum compound.

Next, a method for preparing the contact material will be explained.

The contact between the magnesium alkoxide and the magnesium halide can be achieved by mixing and stirring them in the presence or absence of an inert hydrocarbon, mechanically co-pulverizing them, or the like.

Examples of inert hydrocarbons include hexa〉, heptane, octane, cyclohexane, benzene, toluene, xylene, and the like.

For the contact side between magnesium alkoxide and magnesium halide, 01 to 10 moles of magnesium halide per mole of magnesium alkoxide, preferably 0
．． It is 5 to 2.0 moles. When the contact is made in the presence of an inert hydrocarbon, the hydrocarbon is added per 1 oog of the total amount of magnesium alkoxide and magnesium halide.
It is desirable to use ~1009.

When mechanically co-pulverizing the magnesium alkoxide and magnesium halide, the contact temperature is between room temperature and 200°C.
When mixing and stirring in the presence of the hydrocarbon, it is desirable to carry out the mixing at room temperature to 2'00°C for 1 to 100 hours. Among these contact methods, mechanical co-pulverization is particularly preferred. desirable. Mechanical co-pulverization may be carried out using a common pulverizer used to obtain pulverized products, and examples of such pulverizers include rotary ball mills, vibrating ball mills, impact mills, and the like. The co-pulverization treatment can be carried out, if necessary, under reduced pressure or in an inert gas atmosphere, and in a state where moisture, oxygen, etc. are substantially absent.

The contact material obtained as described above is then contacted with a halogenated hydrocarbon, an electron donating compound and a titanium compound. The town uses the contact method as follows: (1) Bringing the contact material into contact with a halogenated hydrocarbon;
Then, after contacting with an electron donating compound, contacting with a titanium compound, (2) contacting the contact material with an electron donating compound, then contacting with a halogenated hydrocarbon, and then contacting with a titanium compound, 13+ contacting the contact material with a halogenated hydrocarbon;
(4) contacting the contact material, the halogenated hydrocarbon and the electron donating compound simultaneously; and then contacting the titanium compound; (5) contacting the titanium compound; The compound, halogenated hydrocarbon, and titanium compound are contacted simultaneously, and then the electron-donating compound is contacted.

(0) bringing the contact material into contact with a halogenated hydrocarbon;
Preferably, a method is used, in which the electron-donating compound and the titanium compound are then brought into contact at the same time, (7) the contact material, the halogenated hydrocarbon, the electron-donating compound, and the titanium compound are brought into contact at the same time, and more preferably (1), (
2), (3), (4) and (5). The methods (1) to 15j will be explained below.

Method (1) ■ Contacting the contact material with a halogenated hydrocarbon The contact between the melted material and the halogenated hydrocarbon is carried out in the form of a solid or slurry mixture of the contact material and a solid or liquid halogenated hydrocarbon. This can be accomplished by mechanically co-pulverizing a mixture of the above, or by stirring and contacting the mixture with @. Among these, the contact method of mechanical co-pulverization is preferred.

As the halogenated hydrocarbon, any of the above compounds may be used, but hydrocarbons having 2 or more carbon atoms, i.
Halides are preferred. To illustrate them, 1.2-
Ji? Lolethane, 1.1.2-Trichloroethane, 1,
1.2-) dichloroethylene, 1.1.2.2-tetrachloroethane, 1.2.2. '2-tetrachloroethane, pentachloroethane, hexachlorobenzene, 1,
Examples include 2-dichloropropane, hexachloropropylene, octachloropropane, hexachlorobenzene, and the like.

The contact ratio between the contact material and the halogenated hydrocarbon is preferably 0.01 to 20 moles of halogenated hydrocarbon per mole of magnesium alkoxide in the contact material, preferably o, i to 2.
．． It is 0 mole.

In the case of mechanical co-pulverization, the contact between the two may be carried out using a normal pulverizer used to obtain a pulverized product, such as a rotary ball mill, a vibrating ball mill,
Impact mills and the like can be mentioned. The co-pulverization treatment can be carried out, if necessary, under reduced pressure or in an inert gas atmosphere, and in a state where moisture, oxygen, etc. are substantially absent.

In the case of mechanical co-pulverization, the contact temperature is 0 to 200°C, and the contact time is 0.5 to 100 hours. In the case of the contact method using vigorous stirring, the contact temperature is 0 to 200C, and the contact time is 05 to 100 hours.

(2) Contact with an electron-donating compound The contact material of the contact material and the halogenated hydrocarbon (hereinafter referred to as contact material (1)-i) is then brought into contact with an electron-donating compound. The contact +111 may be cleaned with a suitable cleaning agent, such as the inert hydrocarbons mentioned above, before contacting with the electron-donating compound.

The contact between the contact material ft) -1 and the electron-donating compound is
The two may be brought into contact as is, or may be brought into contact in the presence of an inert hydrocarbon and/or a halogenated hydrocarbon. Examples of the contact method include a method of mixing and stirring the two, a method of mechanically co-pulverizing the two, and the like.

As inert hydrocarbons, saturated aliphatic, saturated alicyclic and aromatic hydrocarbons having 6 to 12 carbon atoms such as hexane, heptane, octane, cyclohexane, benzene, toluene and xylene are preferable (hereinafter referred to as the present invention). In the explanation,
Inert hydrocarbons usually refer to these. ). Father, No. 1
As the 0-genated hydrocarbon, any compound can be used as long as it is used in contacting with the magnesium alkoxide.

The contact ratio between the contact substance (11-1 and the electron donating compound is
The electron-donating compound is 0,001 to 10 moles per mole of magnesium alkoxide, preferably tL<HO101 to 5 moles.

In the method of contacting in the presence of a hydrocarbon, when mixing and stirring, it is desirable to use an amount such that the solid substance in the sieve system is 10 to -500 g per 16 of the liquid substance. , the contact temperature at this time is 0 to 20
0°C, preferably 20-150''C, and the contact time is preferably 0.1-20 hours, preferably 5-10 hours.

When co-pulverizing mechanically, the contact material (11+, 100
It is desirable to use 1 to 100 g of the hydrocarbon per gram, and the contact temperature at this time is room temperature to 200 C, the contact time is n,
i~100 hours.

When contacting an electron-donating compound in the absence of a hydrocarbon, it is preferable to use a method of mechanical co-pulverization.
Desirable contact temperatures in this case are room temperature to 20°C, and contact times are + to 100 hours.

(2) Contact with a titanium compound The contact material, the halogenated hydrocarbon, and the electron-donating compound (hereinafter referred to as contact material (1)-2) are then brought into contact with a titanium compound.

The contact material (11-2) may be cleaned with a suitable cleaning agent, such as an inert hydrocarbon as described above, before contacting with the titanium compound.

The contact material (11-2) and the titanium compound may be brought into contact with each other as they are, but they may be mixed and stirred in the presence of a hydrocarbon or halogenated hydrocarbon, or mechanically co-pulverized. It is desirable to do this using a method such as

As the hydrocarbon, saturated aliphatic, saturated alicyclic, and aromatic hydrocarbons having 6 to 12 carbon atoms such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene are preferable. As the halogenated hydrocarbon, any compound can be used as long as it is used in contacting with the magnesium alkoxide.

The ratio of the contacting material (1)-2 and the titanium compound used is as follows: magnesium 1 in the contacting material (11-2)
per gram atom, titanium compound o, 1 gram mole or more,
The Vi is preferably 1 to 5 gmol. When the contact is carried out in the presence of a hydrocarbon and/or a halogenated hydrocarbon, the contact conditions are 0 to 200C for 0.5 to 20 hours, preferably 60 to 150C for 1 to 5 hours.

The amount of hydrocarbon and/or halogenated hydrocarbon used,
Contact material (1)-2 corresponds to liquid substance (hydrocarbon pump/or liquid halogenated hydrocarbon and liquid titanium compound) 1, and it is desirable to use it so that the number is 10 to 5009.

Further, the contact material (1)-2 and the titanium compound may be brought into contact with each other two or more times, and the contact conditions may be the same as those described above.

Method (2) ■ Contacting the contact material with the electron-donating compound The contact between the contact material and the electron-donating compound is carried out in the presence of an inert hydrocarbon, as in the method (1) (■) above. or in the absence of
This can be achieved by a method of mixing and stirring, a method of mechanical co-pulverization, etc.

The contact ratio between the contact material and the electron-donating compound is 1 to 10 moles of the electron-donating compound per 1 mole of magnesium alkoxide in the contact material, preferably 0.01 to 10 moles.
It is 5 moles.

In a method of contacting in the presence of an inert hydrocarbon,
When mixing and stirring, it is desirable to use the hydrocarbon in an amount such that the solid substance in the contact system is 10 to 500 parts per 16 parts of the liquid substance, and the contact temperature in this case is 0 to 500 parts.
200 DEG C., preferably V'i 20-150 DEG C., and the contact time is 0.1-20 hours, preferably 0.5-10 hours. In the case of mechanical co-pulverization, it is desirable to use 1 to 100 g of the hydrocarbon per 100 pieces of the contact material,
The contact temperature at this time is room temperature to 200℃, and the contact time is 0.1
~100 hours.

When an electron-donating compound is contacted in the absence of a hydrocarbon, it is desirable to use a mechanical Ic co-pulverization method, and the desirable contact temperature in this case is room temperature to 200°C, and the contact time is 01 to 100 hours. be.

■ Contact with halogenated hydrocarbon; contact with electron-donating compound (hereinafter referred to as contact +
2) It is called -1. ) and the halogenated hydrocarbon, as in the method (1) (1) above, a solid or slurry mixture of the contact material +2+ -1 and the solid or liquid halogenated hydrocarbon is mechanically brought into contact with the halogenated hydrocarbon. This can be achieved by a method of co-pulverizing or a method of vigorous stirring, but among these methods, a contact method of mechanically co-pulverizing is preferred.

The contact material f21-1 may be cleaned with a suitable cleaning agent, such as an inert hydrocarbon, before being brought into contact with the halogenated hydrocarbon.

The contact ratio between the contact material +2+-1 and the halogenated hydrocarbon is as follows: magnesium alkoxide 1 in the contact material +21-1
The amount is 0.1 to 20 moles, preferably 0.1 to 20 moles, of halogenated hydrocarbon per mole.

The contact conditions such as contact temperature and contact time are preferably the same as those for method (1) (2) above.

■ Contact with the titanium compound The contact between the contact material, the electron-donating compound, and the halogenated hydrocarbon contact material with the titanium compound is as described in (1) above.
It is best for school children to do it in the same way as in the case of the method.

Method (3) ■ Contacting the contact material with the halogenated hydrocarbon □ and contacting the contact material with the halogenated hydrocarbon are carried out in the same manner as in the method (1) (1) above.

(2) Contact with a titanium compound The contact material obtained in the above contact (2) is brought into contact with a titanium compound in the same manner as in the method (2) of fl) above.

■ Contact with the electron-donating compound The contact between the contact material (hereinafter referred to as the contact material (3)) obtained in the above-mentioned contact with the electron-donating compound and the electron-donating compound involves the extraction of inert hydrocarbons and/or halogenated carbonization. This can be achieved by a method of mixing and stirring, a method of mechanical co-pulverization, etc. in the presence or absence of hydrogen.

The contact ratio between the contact material (3) and the electron-donating compound is o, o i mol - 10 mol of the electron-donating compound per 1 gram atom of titanium in the contact material (3), more preferably 000
It is 2 to 5 moles.

In the method of contacting in the presence of hydrocarbons and/or halogenated hydrocarbons, when mixing and stirring the hydrocarbons, the solid substance in the contact system is 1/16 of the liquid substance.
It is desirable to use an amount such that the amount is 0 to 500 g, and the contact temperature at this time is 0 to 200 C, preferably 20 to 1
The temperature is 50 DEG C. and the contact time is preferably 0.1 to 20 hours, preferably 0.5 to 10 hours. When co-pulverizing mechanically, the hydrocarbon is 1 to 1009 g per 131100 g of contact material
It is preferable to use the contact humidity at room temperature to 200℃.
C. The contact time was 01 to 100 hours.

When the electron donating compound is brought into contact with the hydrocarbon in the absence of the hydrocarbon, it is preferable to use a mechanical co-pulverization method, at which time the contact humidity is normal flow to 20D°C, and the contact time is 0.1
~100 hours is terrible.

Further, the material in contact with the electron-donating compound may be further brought into contact with the titanium compound according to the method (2) of fl) above.

, Method (4)■ Contact of the contact material, the halogenated hydrocarbon, and the electron-donating compound The contact of the contact material, the halogenated hydrocarbon, and the electron-donating compound is based on the presence of an inert hydrocarbon. This can be accomplished by mixing and stirring, mechanically co-pulverizing, or the like in the absence of a precipitate.

The contact ratio of the contact material, the halogenated hydrocarbon, and the electron donating compound is preferably 0.01 to 20 moles of the halogenated hydrocarbon, preferably 0.1 to 2.0 mole, and 0.1 to 2.0 mole of the halogenated hydrocarbon per 1 mole of magnesium alkoxide in the contact material. sexual compound o, o
O+~10 moles O, O1~5 moles.

In Method 1 of contacting in the presence of a hydrocarbon, when mixing and stirring, it is desirable to use an amount such that the amount of the solid substance in the contact system is 10 to 5,002 parts per 16 parts of the liquid substance; The actual contact temperature is 0 to 200
℃, preferably 20 to 150℃, and the contact time is 0.
The time is 1 to 20 hours, preferably 0.5 to 10 hours. In the case of mechanical co-pulverization, it is desirable to use 1~'+o op of the hydrocarbon per 100g of solid material, and the contact temperature at this time is room temperature to 200C, and the contact time is 01~1.
00 hours is desirable.

In the case of full contact with No. 5 in the absence of the hydrocarbon, it is desirable to use a method of mechanical co-pulverization, at which time the contact temperature is normal flow to 20 DC, and the contact time is 01 to 100 hours. desirable.

■ Contact with the titanium compound The contact between the contact material, the halogenated hydrocarbon, and the electron-donating compound, and the titanium compound is carried out in the same manner as in the method (1) above. It will be done.

Method (5) ■ Contact with the contact material, halogenated hydrocarbon, and titanium compound Simultaneous melting of the contact material, halogenated hydrocarbon, and titanium compound can be carried out using hexane, heptane, octane, cyclohexane, benzene, toluene, and ghylene. It is carried out by a contact method using mechanical crushing or a contact method involving mixing and stirring in the presence or absence of a hydrocarbon such as.

The proportions of the contact material, halogenated hydrocarbon and titanium compound may be the same as in the method (3) above. That is, per mole of magnesium alkoxide in the contact material, the amount of the halogenated W frozen confection is 0.01 to 20 moles, preferably 05 to 20 moles, and the amount of the titanium compound is 0.1 mole or more, preferably 1 to 5 moles.

Father, contact temperature: 0~200C1 Desired: 20~+50
C. Contact time is 05-100 hours, preferably 1-50 hours.
It's time.

When contacting the hydrocarbon in the presence of a hydrocarbon, the solid substance in the contact system is 10 to 10% of the liquid substance.
It is desirable to use an amount such that the amount becomes 5009.

■Contact with a child-donating compound The contact between the contacting substance, a halogenated hydrocarbon, and a titanium compound simultaneously contacted with an electron-donating compound is carried out in the same manner as in the method (3) above. It will be done.

The solid material not containing the liquid material obtained as described above can be left as is, and the solid material containing the liquid material can be separated from the liquid material to be used as the catalyst component (solid component processing) of the present invention. However, if necessary, it is washed with an inert hydrocarbon and, after drying or as a slurry in an inert hydrocarbon rj3, is subjected to olefin polymerization or contact with an organoaluminum compound. □The solid component technology according to the present invention has a specific surface area of 100 to 65 as measured by the BETI method at the adsorption temperature of liquid nitrogen.
0 m"/9, and the average pore radius is mainly 5 to 20 mm. Its composition is 10 to 20 mm of magnesium atoms, 1 to 15 mm of titanium atoms, and 4 mm of titanium atoms.
The weight range is 0 to 65%, the electron donating compound is 1 to 20% by weight, and other organic compounds are included. The material contains small amounts of halogenated hydrocarbons and/or their conversion substances used in the preparation of solid component (1).

Furthermore, the present invention provides a solid component I obtained by the above method.
The catalyst component (solid component (2)) of the present invention is brought into contact with an organoaluminum compound.

The contact between the solid component I and the organoaluminum compound is achieved by a contact method involving mixing and stirring, a contact method involving mechanical co-pulverization, etc. in the presence or absence of an inert hydrocarbon. As the organoaluminum compound, any of the above compounds can be used, but realkyl aluminum and dialkyl aluminum halide are more preferred. The proportion of the solid component I and the organoaluminum compound used in contact with each other is from 0.05 to 10 g mol, preferably from 0.1 to 5 g mol, of the organoaluminum compound per gram atom of titanium in the solid component I. When contacting is carried out by mixing and stirring in the presence of an inert hydrocarbon, 1 of the inert hydrocarbon is mixed with 10 to 50 of the solid component (2).
0g, more preferably 15 to 2009. The contact temperature is from -50°C to 150°C, more preferably from -20'C.
There is 1000r.

In this case, the contact method is to gradually add a predetermined amount of the organoaluminum compound to the solid component I over a period of 1 minute to 10 hours, preferably 5 minutes to 5 hours, and then bring the compound into contact with the solid component
．． It is desirable to continue stirring and contact for 1 to 20 hours, preferably 0.5 to 10 hours.If the two are brought into contact for a short period of less than 1 minute, the solid component will be split into fine particles and the subsequent solid component preparation will be difficult. At the same time, if this solid component is used to polymerize olefins, a large amount of finely powdered olefin polymers will be produced, which will adversely affect the physical properties of the polymers, the productivity of the polymers, etc., which is undesirable. In the case of mechanical co-pulverization and contact, it is desirable to use 1 to +oo9 inert hydrocarbon per 1100 g of solid component, and the contact temperature in this case is room temperature to 100C, and the contact time is preferably 5 minutes to 2 hours. .

When the contact is carried out without using an inert hydrocarbon, it is preferable to contact by mechanical co-pulverization, and the contact temperature at that time is room temperature to 100°C, and the contact time is preferably 5 minutes to 2 hours.

The contact between the solid component I and the organoaluminum compound may be carried out in the presence of an olefin, and in that case, a contact method of mixing and stirring in the presence of an inert hydrocarbon is desirable. As olefins, in addition to ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
α-olefins such as pentene and 1-octene are used. These olefins are limited to one type, but two or more types may be used. When brought into contact with olefins, the resulting catalyst component prevents fragmentation and refinement caused by organoaluminum compounds,
In addition, the mechanical strength of the catalyst component is improved, and therefore, it is possible to prevent the catalyst component from becoming fine when it is handled, and thereby to prevent the formation of a finely divided polymer.

Examples of the method of contacting the olefin include a method of bringing the solid component I into contact with the organoaluminum compound and then contacting the olefin, a method of bringing the olefin into contact with the solid component I and then contacting the organoaluminum compound, etc. It will be done.

The ratio of organoaluminium and solid component (1) used in this case is the same as in the case where it is not brought into contact with the olefin, and the amount of olefin used is 0.01 to 109 per 11 solid components. The contact time of the olefin varies depending on the amount of olefin used, the contact temperature, the contact pressure of the olefin, etc., but is usually 1 minute to 48 hours. Contact temperature of olefin: 0
~80°C, preferably room temperature ~65°C.

Alternatively, the olefin may be brought into contact with hydrogen in the presence of hydrogen.

In this way, the catalyst component (solid component ■) of the present invention is prepared. The solid component ■ obtained by contacting with an organoaluminum compound in the presence of may be separated from hydrocarbons or may be used as a slurry without separation and used as a catalyst component in the polymerization of olefins. It may be washed with an inert hydrocarbon, and after drying, it may be used for olefin polymerization.

Further, the catalyst component prepared by contacting with an organoaluminum compound may be subjected to polymerization after being stored for a long period of time, or may be subjected to polymerization immediately after preparation.

The solid component according to the present invention has a specific surface area of 0 to 65 as measured by the BETI method at the adsorption temperature of liquid nitrogen.
0 m”/9, the average pore radius is 5-408. Father,
Its composition is 0.2 to 20% by weight of magnesium atoms,
002-15% by weight of titanium atoms, 1-15% of halogen atoms
65% by weight, aluminum atoms are o, o O1~20
% by weight, and contains other organic compounds, etc., and when olefin contact is carried out, the solid component (1) contains 1 to 90% by weight of the olefin polymer.

The catalyst component of the present invention is used in combination with an organoaluminium compound to form a catalyst for homopolymerization of olefins or copolymerization with other olefins.

The organoaluminum compound to be combined with the catalyst component in weighting the olefin may be any of the aforementioned compounds used in pretreating the solid component, but among them:
Trialkylaluminum is preferred, particularly triethylaluminum and b-lisoptylaluminum. These trialkylaluminums may be combined with other organoaluminum compounds such as industrially available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or mixtures or compounds thereof. It can be used in combination with complex compounds, etc.

Furthermore, the organoaluminum compound may be used alone or in combination with an electron-donating compound. ``The electron-donating compound may be the same as the compound that can be used during the treatment of the solid component.

The electron-donating compound may be used when an organoaluminum compound is used in combination with a catalyst component, or may be used after being brought into contact with the organoaluminum compound in advance.

The amount of the organoaluminum compound used in the catalyst component of the present invention is usually 1 to 2,000 g mol, preferably VC 20 to 500 g mol, per 1 gram atom of titanium in the catalyst component.

The ratio of the organoaluminum compound to the electron-donating compound is 01 to 40, preferably 1 as aluminum, to 1 mole of the electron-donating compound.
~25 gram atoms.

The catalyst composed of the catalyst component and the organoaluminum compound (and electron-donating compound) obtained in this way can be used for monoolefins such as ethylene, propylene, 1-butene,
It is useful as a catalyst for homopolymerization of 4-methyl-1-pentene, 1-hexene, 1-octene, etc. or copolymerization with other monoolefins or diolefins, but especially for ethylene polymerization or ethylene polymerization. and α with 5 to 10 carbon atoms
-Excellent performance as a catalyst for random or block copolymerization with olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.

The polymerization reaction may be carried out in either a gas phase or a liquid phase. When polymerizing in a liquid phase, polymers such as normal butane, itbutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, Fluene, xylene, etc. are used. 1 in hydrocarbons and in liquid monomers. The polymerization temperature is usually in the range of -80°C to +1500°C, preferably 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer is controlled by the presence of hydrogen or other known molecular weight regulators. The amount of the other olefin to be copolymerized with the olefin in the copolymerization is usually selected in the range of up to 50% by weight, especially from 0.5 to 15% by weight, based on the olefin. The polymerization reaction using the catalyst system of the present invention may be carried out in a continuous or batchwise reaction, and the conditions may be those commonly used. Father, the copolymerization reaction may be carried out in one step,
It may be done in two or more stages.

Effects of the Invention When the catalyst component of the present invention is used to perform monopolymerization of olefins, particularly ethylene, or copolymerization of ethylene with other olefins, it exhibits high catalytic activity, and the effect of molecular weight adjustment by hydrogen is large. A polymer with a high melt index is easily obtained, and the resulting iIJ polymer exhibits effects such as improved particle properties and high bulk density.

Catalytic activity does not decrease even under high hydrogen partial pressure, and high catalytic activity can be maintained.

In the copolymerization of ethylene and α-olefin,
A low-density copolymer with good copolymerization performance, high bulk density, and low solubility in a solvent can be easily produced in high yield.

EXAMPLES Next, the present invention will be specifically explained using examples and application examples. However, the present invention is not limited only to the examples. In addition, the percentages shown in the examples and application examples (
H) is based on weight unless otherwise specified.

Specific surface area of solid component (S, A, l, pore volume (p, v
) and average pore radius (JP, R, lke, CARLO
The measurements were carried out using a 5ORPTOIJATrC1810 model manufactured by ERBA.

The particle size distribution of the solid component and the catalyst component was measured using a light transmission particle size distribution analyzer model SKN 500 manufactured by Seishin Enterprises.

Polymer melt index (IJI + is AST
According to h4-D125B, temperature 190'C, load 2.1
Measured at 6~. Flow ratio (FRl) is the value obtained by measuring HLlvl■'l at a temperature of +90'C and a load of 21.61c9 in the above MI measurement (MI + quotient,
It represents the outflow ratio of the polymer and is a measure of the molecular weight distribution of the polymer. Father, indicates the proportion of low molecular weight polymer in the polymer / Lumalhexane soluble content (nH8) is the proportion of dissolved chelimer when the polymer is extracted with boiling normal hexane in a modified Soxhlet extractor for 5 hours. be.

The olefin contact amount is the polymer amount (9) relative to the solid component 19 before contact with the olefin, and the i 1J mer amount is the catalyst component 2 N F (2So, aqueous solution and ether/-
The solid component was separated from the polymer, and the separated polymer was washed with ethanol, dried under vacuum at 70° C. for 10 hours, and weighed.

Catalytic activity Kpc minus y IJ mass per gram of catalyst component (9). Solid component active Kctj is the amount of polymer produced per gram of solid component before contact with niolefin (9). Specific activity is 1g of solid component before contact with olefin.
, polymerization time 1 hour, monomer partial pressure during polymerization I H/am
” indicates the amount of polymer produced per unit (9).

Example 1 Contact commercially available magnesium diethoxide 5B9 and anhydrous magnesium chloride 48 g' in a stainless steel (SUS) with a diameter of 12 m.
After placing in a stainless steel (SUS 5 + 6) mill pit with an internal volume of 1 ton containing 540 5161 bowls, and attaching this mill pot to a shaker, it was shaken for 4 hours and co-pulverized. ,-xachloroethane 52
g [Gang(OC2H512/Mgct2/C2C/-6(
Molar ratio) = 1/1/0.24) was added and co-pulverized for 15 hours, and 15 ml of ethyl benzoate was further added and co-pulverized for 15 hours to obtain a pulverized product.

10 grams of the pulverized material obtained above was heated at 50 °C under a nitrogen gas atmosphere.
Put it in an occ flask and add it to this) Rouet> I O'O
ml, and titanium tetrachloride 50m/! Add 9'5C to 2
After stirring for an hour and making contact, excess liquid was removed and the solid solid substance was heated at 65°C with +501nl of n-hexane.
The solid component (1) was obtained by washing the product six times with water and drying at 50° C. for 1 hour under reduced pressure. The composition and physical properties of this solid component were as shown in Table 1.

Example 2 The order of contacting monoxachloroethane and ethyl benzoate with the contact product of magnesium jetoxide and magnesium chloride in Example 1 was changed to first contacting the contact product with ethyl benzoate and then contacting the contact product with hexachloroethane. Solid component (2) was obtained in the same manner as in Example 1 except for the following steps. The composition and physical properties of this solid component were as shown in Table 1. Example 5 A contact mixture of magnesium jetoxide, unsium chloride and hexachloroethane was obtained in the same manner as in Example flJ1. 10 g of this contact material was heated for 5 minutes in a nitrogen gas atmosphere.
0QCC flask, add 1) luene [110
After adding m1 and 50 - of titanium tetrachloride and stirring at 95°C for 2 hours to bring them into contact, excess liquid was removed. The solid material was then washed six times at 65C with 150 ml of n-hexane each. Subsequently, this washed product was treated with ethyl benzoate Q59, n-hexane 150 + ni'tjJ[le5
The contact was stirred for 2 hours at 0C. After that, each 150-
The solid component (3) was washed four times with n-hexane and dried under reduced pressure at 50C for 1 hour. The composition and physical properties of this solid component are as shown in Table 1.

Example 4 A contact product of magnezi 2mushi ethoxide, magnesium chloride and hexachloroethane was obtained in the same manner as in Example 1. This contact material 109 was heated at 500 CC under a nitrogen gas atmosphere.
1[]0d2f of toluene and 06 ml of ethyl benzoate were added thereto, stirred at 65° C. for 2 hours to bring them into contact, and excess liquid was removed. The solid material was then washed twice with 150 liters of toluene each. Subsequently, titanium tetrachloride treatment was performed in the same manner as in Example 1 to obtain a solid component (4). The composition and notes of this solid component (4) were as shown in Table 1.

Examples 5 to 8 Solid components (5) to (8) were obtained in the same manner as in Practical Example 1, except that the following electron-donating compound was used in place of ethyl benzoate in Example 1. Each solid component The composition and physical properties were as shown in Table 1.

5 Ethyl anisate 6, Methysate p-toluate 7 Dibutyl ether 8 Te) Lahydrofuran Comparative Example 1 Only magnesium jetoxide was placed in the mill pot used in Example 1 and shaken for 15 hours.

The obtained pulverized product was contacted with titanium tetrachloride in the presence of toluene in the same manner as in Example 1. The resulting contact material was treated in the same manner as in Example 1 to obtain a solid material. The composition and physical properties of this solid material were as shown in Table 1.

Comparative Example 2 160 g of magnesium jetoxide and 209 g of ethyl benzoate were added to the mill bottle used in Example 1, and the mixture was shaken for 15 hours. The obtained pulverized product (most of it was in the form of lumps and could not be obtained in powder form) was contacted with titanium tetrachloride in the presence of toluene in the same manner as in Example 1. The resulting contact material was treated in the same manner as in Example 1 to obtain a solid material.

The composition and physical properties of this solid material were as shown in Table 1.

Example 9 Solid component (1) 59 of Example 1 was placed in a 200 CC flask under a nitrogen gas atmosphere, and n-heptane IQQCC was added.
was added to make a slurry. While stirring this slurry at room temperature, 65 mmol of triethylaluminum was gradually added dropwise over 1 hour, and stirring was continued for 2 hours after one drop.

Then, the supernatant liquid was removed, washed four times with 10 ml each of D-hexane, and further dried to obtain a solid component (9).

The composition and physical properties of this solid component were as shown in Table 1.

Example 10 Solid component (7) 59 obtained in Example 7 was added to triethylaluminum used in Example 9.

Solid component 00) was obtained in the same manner as in Example 9 except that 5.0 mmol of diethylaluminum chloride was used.

The composition and physical properties of this solid component are shown in Table 1.

Example 11 In place of the triethylaluminum used in Example 9, diethylaluminum chloride was used to prepare the solid component αυ in the same manner as in Example 9, except that 6.5 mmol of the (i:i+ complex) of moro-butyl ether was used. The composition and physical properties of this solid component were as shown in Table 1.

Example 12 The solid component +3159 obtained in Example 5 was placed in a nitrogen gas atmosphere fi
Place n-hexane 1s in a flask with %'0 OCC under
occ was added to make a slurry. While stirring this slurry at room temperature, 4.8 mmol of triisobutylaluminum was added dropwise over 2 hours, and the slurry was stirred for 1 hour after the dropwise addition.

Ethylene was then introduced at normal pressure while stirring at room temperature.
0.5 g of ethylene was contacted per +311 g of solid component.

Thereafter, the supernatant liquid was removed, washed four times with 150 g of n-hexane, and further dried to obtain solid component a. The composition and physical properties of this solid component were as shown in Table 1. This solid component also contained 22% ethylene polymer.

The average particle diameters of the solid component (3) and α area were 11.5μ and 14.5μ. This solid component (3) and liisobutylaluminum (organoaluminum compound used in the polymerization of color olefin) and (At/Ti=+50 (atomic cc
When brought into contact with l l 85 C, the average particle size of solid component (3) decreases to 8.2 μ and is refined by the organoaluminum compound, but solid component a3 remains unchanged at 14.0 μ.

47 Application example 1 Copolymerization of ethylene and 1-butene A stainless steel (SUS) with an internal volume of 1.56 equipped with a stirrer
In a 516+ autoclave under a nitrogen gas atmosphere,
Using the solid component obtained in Example 1 as a catalyst component, To, 2
m9,) diisobutylaluminum 0. Fumi9 was added, and the polymerization system was heated to 80°C. Next, hydrogen partial pressure 1.
After hydrogen was introduced until the partial pressure of ethylene reached 2 kg/am'', ethylene was introduced until the partial pressure of ethylene reached 5 kg/am'', and 209 g of 1-butene was further added. 1 while continuously supplying ethylene to keep the total pressure of the polymerization system constant.
Time polymerization was performed. After the polymerization was completed, the polymerization solvent, unreacted ethylene and 1-butene were purged, and the white powdery polymer was taken out and dried at 70°C under reduced pressure for 10 hours. '[13.8, FR26, bulk density 0.589/
cc, true density 0, 9 2 5 97 cc ethylene-
1-Butene copolymerization with 1449 (catalyst specific activity 4.6 9
0) Obtained. Also, the n-hexane soluble portion of the polymer (
n [(S) was 3.0%.

Application example 1 was used, except that the solid components obtained in Examples 2 to 12 and Comparative Examples 1 and 2 were used as catalyst components, and the type and amount of como/mer and hydrogen partial pressure were as shown in Table 2. Ethylene copolymerization was carried out in the same manner. The polymerization conditions and polymerization results are shown in Table 2. When the catalyst component of the present invention is used, compared to the catalyst component of the comparative example, a copolymer with higher catalytic activity, higher polymer bulk density, and lower density is produced, and the solvent soluble content of the copolymer is higher. It can be seen that there are few

Ethylene polymerization was carried out by aSC in the same manner as in Application Example 1, except that the solid components obtained in Examples +, 5, 7, and 12 were used as catalyst components, and 1-butene was not used.

The results are shown in Table 2. Further, the average particle size of the polymer obtained when using the organoaluminum compound and the solid component az treated with olefin is 550μ,
The fine powder gelimer with a mesh size of 150 mesh or less is 4 inches, but when solid component (3) without treatment is used, the average particle size of the obtained polymer is 250μ, and the fine powder gelimer with a mesh size of 150 mesh or less is 16 inches. Ta.

Application Example 19 In the autoclave used in Application Example 1, 10.2 m9. ) diisobutylaluminum 0 fumi9 rnI! ．． was charged, and the temperature of the polymerization system was raised to 75°C. Next, the hydrogen partial pressure is 0. After introducing hydrogen to a pressure of 15 rcg/cm, ethylene was introduced until the partial pressure of ethylene reached 3 kg/cm, and then 50 rcg/cm of 1-butene was introduced.
9 7J11. In order to keep the total pressure of the polymerization system constant,
Polymerization was carried out for 15 minutes while continuously supplying ethylene. Subsequently, hydrogen was introduced so that the hydrogen partial pressure became 5.Q kg 7 cm, and 209% of 1-butene was added.
Polymerization was continued for an additional 70 minutes while continuously supplying ethylene to keep the polymerization pressure constant.

After the polymerization is completed, the process is carried out in the same manner as in Application Example 1, and the powdered ethylene-1-butene copolymer is converted to 1679 ( , Kc
16570, specific activity 5870j was obtained. The obtained copolymer was uto. +sa, FR75, bulk density 0, 5
5 97cc, true density 0. It was 9 2 8 97cc.

Procedural amendment (method) % formula % 1, Indication of case 1981, 1J Patent Application No. 227489 2, 56
+yln name+h. Catalyst component for olefin polymerization 3, relationship with the case of the person making the amendment Patent applicant 4, agent ('', Address: No. 16-2, Toramon-chome, Minato-ku, Tokyo Z subject of amendment (1) ``'' in the specification "Title of the Invention" column (2) Contents of the amendment to the power of attorney a (1) "Catalyst component for olefin polymerization (2)" on the second line of page 1 of the specification is corrected to "catalyst component for olefin polymerization."

(2) Supplement the power of attorney with the attached document.

Claims (1)

[Scope of Claims] (I) A catalyst component for olefin polymerization, which is obtained by contacting a contact product of a magnesium alkoxide with a magnesium halide, a halogenated hydrocarbon, a turtle donating compound, and a titanium compound. (2) A catalyst component for olefin polymerization prepared by contacting an organic aluminum compound with a solid component obtained by contacting a contact product of magnesium alkoxide with a magnesium halide, a halogenated hydrocarbon, a sleep-donating compound, and a titanium compound. .