JPS59122504A - 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, a halogenated hydrocarbon, an electron donor, and a Ti compound with each other. CONSTITUTION:The objective catalyst component is prepared by contacting (A) a magnesium alkoxide (preferably the one thermally dried and pulverized under reduced pressure), (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). Preferably, the components (A)-(D) are brought into contact with each other successively in the order. The catalyst component is usually combined with an organic Al compound and used for the (co)polymerization of an olefin. EFFECT:A polymer having high melt index can be produced easily.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a catalyst component for olefin polymerization, and more particularly to a catalyst component capable of producing an olefin homopolymer or copolymer having a high bulk density in high yield.゛Background technology Conventionally, olefins such as ethylene homopolymerization or α
- Catalyst components containing titanium compounds are widely known as copolymerization catalysts with olefins. In order to increase the activity of this catalyst or to 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. It is being

For example, a method of reacting a magnesium oxygen-containing compound with a halogenating agent and then contacting it with a titanium halide (JP-A-47-8595 λ, after co-pulverizing a hydroxyl group-containing magnesium compound and a magnesium alkoxide, A method of bringing titanium halides into contact (Japanese Patent Publication No. 46-540.98), a method of co-pulverizing magnesium halides, magnesium alkoxides and titanium halides (JP-A-51-80383-2, Magnesium 1um halogen However, a method is known in which the compound and the titanium compound are all co-pulverized and then reacted with titanium tetrahalide (JP-A-55-151011, etc. 2). 1. Although the catalytic activity is improved, the bulk density of the obtained polymer is low and the productivity of the polymerization equipment is reduced.
■If the polymerization takes a long time, the activity of the catalyst will decrease drastically. ■If hydrogen is used as a molecular weight regulator, the effect of controlling the molecular weight will be small. Requires polymerization temperature, ■ has low reactivity with other olefins as comonomers in copolymerization and therefore requires high comonomer concentrations;
■If the comonomer content in the comonomer is increased and the density is lowered, the bulk density of the copolymer will also decrease, and a large amount of solvent-soluble low molecular weight polymer will remain, resulting in a high yield of the copolymer. There are still problems such as inability to produce.

DISCLOSURE OF THE INVENTION OBJECTS OF THE INVENTION The present inventors have solved the above problems, especially olefin copolymers,
For example, as a result of intensive study to solve the problems in producing a copolymer of ethylene and α-olefin, we found that magnesium alkoxide, halogenated hydrocarbon, electron donating compound, and titanium compound! When a solid component obtained by contacting the solid component 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, homopolymerization of olefins and the combination of olefins and other olefins are possible. The present invention was completed by discovering that copolymerization proceeds effectively.

Summary of the Invention The present invention provides (1) a catalyst component for olefin polymerization made by contacting a magnesium alkoxide, a halogenated hydrocarbon, an electron-donating compound, and a titanium compound; (2) a magnesium alkoxide, a halogenated hydrocarbon, an electron-donating compound; The gist of the present invention is a catalyst component for olefin polymerization, which is obtained by contacting an organic aluminum compound with a solid component obtained by contacting a compound and a titanium compound.

Raw Materials for Preparing Catalyst Component 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 (OR) (OR'J. In the formula, R and R' have 1 to 20 carbon atoms, preferably 1 to 1 carbon number. ~10 alkyl, alkenyl, cycloalkyl, aryl, aralkyl groups. R and R' may be the same or different.

Examples of these compounds include Mg(00Hs)2.

Mg(OCzHs)z, Mg(OCHx)
(OCzHs), Mg(Oi-oaH7n2゜Mg
(003H7)2・Mg (004H9)2・Mg(0
1-04Hs)z・Mg(004H*n (Oi -0
4Hg), Mg (QC!4Hg) (o
sec-C! 4H9).

Mg(OC'gH1a)z p Mg(OO%y)z
a Mg(OOaHn2.

Mg(OOeHsh, Mg(00eH40Hzλ
z, Mg(OCHtCeHs)z, etc.

When using these magnesium alkoxides, 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.

The halogenated hydrocarbon used in the present invention has 1 to 1 carbon atoms.
Specific examples of these compounds are mono- and polyno-logene substituted products of two saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons, for aliphatic compounds, methyl chloride, methyl bromide, Methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-short ethane, methylchloroform, methylbromoform, methyliodoform, 1.1.2'-)dichloroethylene, 1,1.2-)lipromoethylene, 1,1, 2
．． 2-tetrachloroethylene, pentachloroethane, hexabromoethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloroopan, decabromobutane, chlorinated paraffin Compounds include chlorocyclopropane, tetrachlorocyclobencune, hexachlorobencdiene, hexachlorocyclohexane; aromatic compounds include chlorobenzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, Examples include bensitrichloride, p-chlorobenzotrichloride, and the like.

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

(3) Titanium compound The titanium compound wJ is a compound of divalent, trivalent, and tetravalent titanium, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorjetoxy. Titanium, dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortriptoxytitanium, tetrabutoxytitanium, titanium trichloride and the like can be mentioned.

Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlor, dibutoxytitanium, and dichlorodiphenoxythicone are preferred, and titanium tetrachloride is particularly preferred.

(4) Electron-donating compounds Examples of the electron-donating compounds used in the present invention include carboxylic acids, carboxylic acid esters, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, and alcoholates. phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or 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 cyclohexanecarboxylate, ethyl benzoate, p -Ethyl methoxybenzoate, methyl p-methylbenzoate, ethyl p-tertiary butylbenzoate, dibutyl phthalate, dibutyl phthalate, α
Examples include, but are not limited to, -ethyl naphthoate. Among these, alkyl esters of aromatic carboxylic acids, particularly alkyl esters of nuclear substituted benzoic acids having 1 to 8 carbon atoms such as fN, aromatic acid, dp-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 methanol, ethanol, gropanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octatool, 2-
These include ethylhexanol, cyclohexynol, benzyl alcohol, and allyl alcohol. Ethers are represented by the general formula ROR'. In the formula, R and R' are alkyl, alkenyl, cycloalkyl, aryl, and aralkyl having 1 to 12 carbon atoms, and R and R' may be the same or different. Cyclic ethers can also be used. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl ether, butyl allyl ether, and diphenyl ether. , anisole, ethyl phenyl ether, tetrahydrofuran, 1,
4-dioxane, etc.

The organoaluminum compound has the general formula RnAtX5-n (
However, R represents an alkyl group or an aryl group, or a halogen atom, an alkoxy group, or a hydrogen atom, and n is + n≦6
Any number in the range . ) is also shown as
For example, carbon atoms of 1 to 18, such as trialkylaluminium, dialkylaluminum monohalide, monoalkylaluminum civalide, alkyl aluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride;
As the freezing agent, an alkylaluminum compound having 2 to 6 carbon atoms, or a mixture or complex compound thereof is particularly preferable. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylaluminum chloride, etc. Monoalkylaluminum dino-rides such as dialkylaluminum monohalide, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, alkylaluminum sesquino 1lide such as ethylaluminum sesquichloride, dimethylaluminum Methoxide, diethyl aluminum iodide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxide such as dibutyl aluminum phenoxide, dimethyl aluminum hydride, diethylaluminium hydride, di Dialkyl aluminum rhamno hydride such as propyl aluminum rhamno hydride and diisobutyl aluminum hydride are mentioned.

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

In addition, these dialkyl aluminum monohalide aluminum compounds, such as triethyl aluminum, triisobutyl aluminum, which are industrially easily available,
It can be used in combination with ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide 1, diethylaluminium hydride, or a mixture or complex compound thereof.

Preparation of Catalyst Component The catalyst component of the present invention comprises a magnesium alkoxide, a halogenated hydrocarbon, an electron-donating compound, and a titanium compound.
Solid component I obtained by contacting with lJ and solid component obtained by further contacting this solid component I with an organoaluminum compound], magnesium alkoxide, halogenated hydrocarbon, electron donating compound, and titanium compound. The contact method is as follows: (11) Bringing the magnesium alkoxide into contact with the rogenated hydrocarbon, then contacting the electron-donating compound, and then contacting the titanium compound. (3) magnesium alkoxide and a titanium compound after contacting with a hydrogenated hydrocarbon;
(4) contacting a logenated hydrocarbon, then contacting a titanium compound, and then contacting an electron-donating compound;
A magnesium alkoxide, a halogenated hydrocarbon, and an electron-donating compound are brought into contact at the same time, and then a titanium compound is brought into contact. (6)
) Contacting a magnesium alkoxide and a halogenated hydrocarbon, and then contacting an electron donating compound and a titanium compound simultaneously; (7) A method comprising simultaneously contacting a magnesium alkoxide, a halogenated hydrocarbon, an electron donating compound, and a titanium compound. Preferably used, and more preferably (1).

These are methods (2), (31, (41) and (5).

The methods (1) to (5) will be explained below.

Method (1) ■ Contact between magnesium alkoxide and halogenated hydrocarbon Contact between magnesium alkoxide and halogenated hydrocarbon involves mixing a solid or slurry mixture of magnesium alkoxide and a solid or liquid halogenated hydrocarbon. This can be accomplished by mechanical co-grinding or simply stirring and contacting. Among these, a contact method of mechanical co-pulverization is preferred.

As the halogenated hydrocarbon, any of the above-mentioned compounds may be used, but polyhalides of hydrocarbons having 2 or more carbon atoms are preferred. Examples of these are 1,2-dichloro-ethane, 1i,2-)dichloroethane, 1゜1
．． 2-trichloroethylene, i, I, 2.2-tetrachloroethane, I, 2,2.2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,2
- Dichloropropane, hexachloroethane, octachloropropane, hexachlorobenzene, etc. The contact ratio of magnesium alkoxide and halogenated hydrocarbon is 0.01 to 20 mol of halogenated hydrocarbon per mol of magnesium alkoxide, Nozomi Shiguni 0.1~
It is 20 moles.

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 α5 to 100 hours. Further, in the case of a contact method of simply stirring, the contact temperature is 0 to 200°C and the contact time is 0.5 to 100 hours.

■ Contact with an electron-donating compound The contact material of the magnesium alkoxide and the halogenated hydrocarbon (hereinafter referred to as contact material (1)-1) is then brought into contact with an electron-donating compound. Before contacting with the chemical compound, it may be washed with a suitable detergent, such as the inert hydrocarbons mentioned above.

Contacting substance (1) -1 and the electron-donating compound may be brought into contact with each other to that extent, 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 the inert hydrocarbon, saturated aliphatic, saturated alicyclic and aromatic hydrocarbons having 6 to 12 carbon atoms such as hexane, hegetane, octane, cyclohexane, benzene, toluene and xylene are preferable (hereinafter referred to as the present invention). (In the description of the above, inert hydrocarbons usually refer to these.) Further, as the halogenated hydrocarbon, any compound can be used as long as it is a compound used when bringing it into contact with the above-mentioned magnesium alkoxide. The contact ratio of contact substance (1)-1 with the electron donating compound is 001 to 10 moles, preferably 1 to 001 to 5 moles of the electron donating compound Q per 1 mole of magnesium alkoxide.

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 contact system is 910 to 500 tons of liquid substance 1. The contact temperature is 0 to 200℃
, preferably at 20-150°C, contact time 0.1
~20 hours, preferably 0.5 to 10 hours. When co-pulverizing mechanically, contact objects (11-1100f, υ,
It is desirable to use the hydrocarbon in an amount of α1 to 100, and the contact temperature in this case is room temperature to 200°C, and the contact time is α1 to 100.
It's time.

When contacting an electron-donating compound in the absence of a hydrocarbon, it is preferable to use a mechanical co-pulverization method.
In this case, the desirable contact temperature is room temperature to 200°C, and the contact time is 0.1 to 100 hours.

■ Contact magnesium alkoxide with titanium compound 1. Contact material with halogenated hydrocarbon and electron donating compound (hereinafter referred to as contact material (1) -
It is called 2. The titanium compound is then contacted with a titanium compound. Contact article (1)-2 may be cleaned with a suitable cleaning agent, such as the inert hydrocarbons mentioned 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. It is preferable to use a method such as pulverization.

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. In addition, as norogenated hydrocarbons,
Any compound used in contacting with the magnesium alkoxide can be used.

The proportion of the contact material (11-2) used in contact with the titanium compound is as follows: magnesium 1 in the contact material (1)-2
0.1 gram mole or more of titanium compound per gram atom,
It 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 condition is α5 to 20 hours at 0 to 200°C, preferably 1 to 5 hours at 60 to 150°C.

The amount of hydrocarbon and/or halogenated hydrocarbon to be used is 17 to 5002, where 11-2 is a liquid substance (hydrocarbon and/or liquid halogenated hydrocarbon and liquid titanium compound). It is desirable to use it as follows.

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) ■ Contact between magnesium alkoxide and electron-donating compound The contact between magnesium alkoxide and electron-donating compound is carried out in the presence of an inert hydrocarbon, as in method (1) (■) above. Alternatively, this can be achieved by a method of mixing and stirring, a method of mechanically co-pulverizing, etc. in the absence of such a material. The contact ratio between the magnesium alkoxide and the electron-donating compound is 0.000000000000000000000000000000000000000000000000 per 1 mole of magnesium alkoxide.
00+ to 10 moles, preferably α01 to 5 moles.

In a method of contacting in the presence of an inert hydrocarbon,
When mixing and stirring the hydrocarbon, it is desirable to use an amount such that the solid substance in the contact system is 10 to 50 of the liquid substance, and the contact temperature in this case is 0 to 50.
The temperature is 200°C, preferably 20 to 150°C, and the contact time is α1 to 20 hours, preferably α5 to 10 hours. For mechanical co-milling, magnesium alkoxide 1
It is desirable to use the hydrocarbons 1 to 1001, with the contact temperature being room temperature to 200°C and the contact time being [L1 to 100 hours].

When contacting an electron-donating compound in the absence of a hydrocarbon, it is preferable to use mechanical co-pulverization throughout the process.
In this case, the desirable contact temperature is room temperature to 200°C, and the contact time is a1 to 1011 hours.

■ Contact with halogenated hydrocarbon The contact between the contact material of magnesium alkoxide and the electron donating compound (hereinafter referred to as the contact material (21-+)) and the halogenated hydrocarbon is the same as in the method (1) above. This can be achieved by mechanically co-pulverizing a solid or slurry mixture of a contact material (2i-1 and solid or liquid) and a logenated hydrocarbon, or by simply stirring it. Of these, a mechanical co-grinding contact method is preferable.Contacting material (2)-1 is a suitable cleaning agent, such as an inert hydrocarbon, before being brought into contact with the halogenated hydrocarbon. You can also wash it with

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)
0.01 to 20 mol of 10-genated hydrocarbon,
Desirably, the amount is 0.1 to 20 mol. The contact conditions such as contact temperature and contact time are preferably the same as those for method (1) (2) above.

■ Contact with titanium compounds Contact of magnesium alkoxide, electron-donating compounds, and halogenated hydrocarbons with titanium compounds is as follows:
It is desirable to carry out the same method as in method (1) (2) above.

Method (3) ■ Contact between magnesium alkoxide and 7-logenated hydrocarbon The contact between magnesium alkoxide and 7-logenated hydrocarbon is carried out in the same manner as in 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 (1) (1) above.

■ Contact with the electron-donating compound The contact material (hereinafter referred to as contact material (3)) obtained in the above-mentioned contact with the electron-donating compound is brought into contact with the electron-donating compound. 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 as follows:
per gram atom of titanium in the melt (3), the electron-donating compound [101 mol to 10 mol, more preferably [10
It is 2 to 5 moles. In the method of contacting in the presence of a hydrocarbon and/or halogenated hydrocarbon, when mixing and stirring, the solid substance to be added to the contact system is such that the liquid substance 1 is in the range of 10 to 6001. It is desirable to use an amount of
, preferably 20 to 15 (Ic, contact time Fi1
The time is 1 to 20 hours, preferably 0.5 to 10 hours. When co-pulverizing mechanically, contact material (3) 100 t”
4. It is desirable to use 1 to 100 f of the hydrocarbon,
The contact temperature at this time is room temperature to 200'C1 contact time is I]
, 1 to 100 hours is desirable.

When the electron-donating compound is brought into contact with the hydrocarbon in the absence of the hydrocarbon, it is preferable to use a method of mechanical co-pulverization, at which time the contact temperature is room temperature to 200°C, and the contact time is α1.
~100 hours is desirable.

Further, the material in contact with the electron-donating compound may be further brought into contact with the titanium compound according to the method (1) (1) above.

Method (4)■ Contact of magnesium alkoxide, halogenated hydrocarbon, and electron-donating compound The contact of magnesium alkoxide, halogenated hydrocarbon, and electron-donating compound is carried out in the presence or absence of an inert hydrocarbon. Under,
This can be achieved by a method of mixing and stirring, a method of mechanically co-pulverizing, or the like. The contact ratio of magnesium alkoxide, halogenated hydrocarbon and electron-donating compound is 11 halogenated hydrocarbons per mol of magnesium alkoxide.
01 to 20 moles, preferably 0.1 to 2.0 moles, and the electron donating compound preferably 0.01 to 10 moles, preferably 0.01 to 5 moles.

In the method of contacting in the presence of hydrocarbons, when mixing and stirring are carried out, the amount of solid material in the contacting system is 10 ~! It is preferable to use an amount such that 100 f, and the contact temperature at this time is 0 to 200 f.
℃, preferably 20-150℃, contact time 01
~20 hours, preferably 1 hour is 0.5 to 10 hours. In the case of mechanical co-pulverization, it is desirable to use 1 to 100 f of the hydrocarbon per 1002 of the solid material, and in this case, the contact temperature is preferably room temperature to 200° C., and the contact time is preferably 0.1 to 100 hours.

When all six components are brought into contact in the absence of the hydrocarbon, it is preferable to use a mechanical co-pulverization method, in which the contact temperature is room temperature to 200°C, the contact time is Q, and 1 to 100 hours. desirable.

■ Contact with a titanium compound: The simultaneous contact of the six components (magnesium alkoxide, halogenated hydrocarbon, and electron-donating compound) with a titanium compound is carried out in the same manner as in the method (1) above. It is done.

Method (5)■ Contact with magnesium alkoxide, halogenated hydrocarbon, and titanium compound Simultaneous contact of magnesium alkoxide, halogenated hydrocarbon, and titanium compound can be carried out using hexane, hegetane, octane, cyclohexane, benzene, toluene, xylene, etc. The contact method is carried out by mechanical grinding or mixing and stirring in the presence or absence of a hydrocarbon.

The proportions of magnesium alkoxide, -logenated hydrocarbon and titanium compound may be the same as in the method (3) above. That is, per mol of magnesium alkoxide, the amount of halogenated hydrocarbon α is 01 to 20 mol, preferably 0.5 to 20 mol, and the titanium compound is 0.1 mol or more, preferably 1 to 5 mol.

Further, the contact temperature is 0 to 200°C, preferably 20 to 150°C.
℃, contact time is 0.5 to 100 hours, preferably 1 to 5
It is 0 hours.

In the case of contacting the hydrocarbon in the presence of a hydrocarbon, the solid substance in the contacting system may cause the liquid substance 1 to
It is desirable to use an amount such that 3002.

(2) Contact with an electron-donating compound The simultaneous contact of the magnesium alkoxide, halogenated hydrocarbon and titanium compound with the electron-donating compound is carried out in the same manner as in the method (3) above.

The solid substance that does not contain a liquid substance obtained as described above is left as is, and the solid substance that contains a liquid substance is separated from the liquid substance to form the catalyst component (solid component 1) 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, is subjected to olefin polymerization or contact with an organoaluminum compound.

The solid component I according to the present invention has a specific surface area of 20 as measured at the adsorption temperature of liquid nitrogen by the Pella l-(BFiT) method.
0-650 m27f, average pore radius mainly 5-2
It is 0 large. The composition of the housing is 10 to 10 magnesium atoms.
The content is 200 to 20% by weight, 1 to 15% by weight of atoms, 40 to 650 to 65% by weight of halogen atoms, 1 to 20% by weight of donor compounds, and other organic compounds. The material contains small amounts of halogenated hydrocarbons used in the preparation of solid component I and/or their conversion substances.

Furthermore, the present invention provides solid component 1 obtained by the above method.
It is made into a catalyst component (solid component I) of the present invention by contacting with a 't-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 trialkylaluminum and dialkylaluminum halide are more preferred. The proportion of the solid component (I) and the organoaluminum compound used in contact with each other is 0.05 to 10% of the organoaluminum compound per 1 gram atom of titanium in the solid component I.
gram mol, preferably 0.1 to 5 gram mol.

If the presence of an inert hydrocarbon is brought into contact with mixing and stirring, the inert hydrocarbon 1 is added to the solid fraction 1
-6009, more preferably 15-200.

The contact temperature is -60°C to 150°C, more preferably -20°C.
℃~100℃. In this case, the contact method is to add a predetermined amount of organoaluminum compound to the solid component l for 1 minute to
Gradually add and contact for 10 hours, preferably 5 minutes to 5 hours, and continue for 0.1 to 20 hours, preferably 0.5 hours.
It is desirable to continue stirring and contact for 5 to 10 hours,
If the two are brought into full contact for a short period of less than 1 minute, the solid component I will split into fine particles, making it difficult to handle the subsequent preparation of the solid component.At the same time, if the solid component I is used to polymerize olefins, a finely powdered olefin polymer will be produced. is produced in large amounts, which is undesirable because it adversely affects the physical properties of the polymer, the productivity of the polymer, etc.

In the case of mechanical co-grinding and contact, the solid component 1100
It is desirable to use 1 to 100 f of an inert hydrocarbon per r, and the contact temperature at this time is preferably room temperature to 100°C, and the contact time is preferably 5 minutes to 2 hours. In the case of contacting without using an inert hydrocarbon, it is preferable to contact by mechanical co-pulverization, and in this case, the contact temperature 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. In addition to ethylene, the olefins include propylene, I-7
"7-one, 1-bentene, 1-hexene, 4-methyl-
α-olefins such as 1-pentene and 1-octene are used. These olefins are not limited to one type, and two or more types may be used. When brought into contact with olefins, the resulting catalyst component completely prevents fragmentation and fineness caused by the organoaluminum compound, and also improves the mechanical strength of the catalyst component, thus preventing the fineness of the catalyst component that occurs when handling the catalyst component. As a result, the formation of fine powder polymer can be prevented.

Examples of methods for contacting olefins include a method in which the solid component I is brought into contact with the organoaluminum compound and then the olefin is brought into contact, a method in which the solid component (I) is brought into full contact with the olefin, and then a method is brought into contact with the organoaluminum compound in its entirety. can be mentioned.

In this case, the ratio of organoaluminum to solid component 1 used is the same as in the case where it is not brought into contact with olefin, and the amount of olefin used is 0.01 to jOf per 111 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. The contact temperature of olefin is 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 ①) of the present invention is prepared, but the solid component ② obtained by contacting with the organoaluminum compound without using an inert hydrocarbon is left in the casing as it is.
The solid component obtained by contacting with an organoaluminum compound in the presence of an inert hydrocarbon may be separated from the hydrocarbon or left in a slurry state without separation and used as a catalyst component in the polymerization of olefins. , or, if necessary, after washing with an inert hydrocarbon and further 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 (1) according to the present invention has a specific surface area of 0 to 6 as measured at the adsorption temperature of liquid nitrogen by the BET method.
50 m27 f, average pore radius 5-4QA.

The composition is n, 2 to 20% by weight of magnesium atoms, α02 to 15% of titanium atoms, 1 to 65% of halogen atoms, 1001 to 20% of aluminum atoms, and 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.

Olefin Polymerization Catalyst The catalyst component of the present invention is combined with an organoaluminum compound to form a catalyst for the homopolymerization of olefins or copolymerization with other olefins.

Organoaluminum Compound The organoaluminum compound to be combined with the catalyst component when polymerizing the olefin may be any of the above-mentioned compounds used when pretreating the solid component, but among them:
Trialkylaluminum, particularly triethylaluminum and triisobutylaluminum, are preferred. These trialkylaluminums may also be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium chloride, or mixtures or complexes thereof. It can be used in combination with other compounds.

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 solid components.

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

The amount of the organoaluminum compound to be used in the catalyst component of the present invention is usually 1 to 2000 g mol, particularly preferably 20 to 500 g mol, per gram atom of titanium in the catalyst component.

Further, the ratio of the organoaluminum compound to the electron donating compound is selected within the range of 0.1 to 40, preferably 1 to 25 g atoms of the organoaluminum compound as aluminum per mole of the electron donating compound.

Polymerization of olefins The catalyst composed of the catalyst component and the organoaluminum compound (and electron-donating compound) thus obtained can be used to polymerize monoolefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1 - It is useful as a catalyst for the homopolymerization of hexene, 1-octene, etc. or copolymerization with other monoolefins or diolefins, but especially for the homopolymerization of ethylene or α of ethylene and 3-10 carbon atoms.
- It shows extremely excellent performance as a catalyst for random or block copolymerization with olefins such as propylene, I-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, inert carbon such as normal butane, isophane, normal pentane, impentane, hexane, heptano, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen chloride and in liquid monomers. The polymerization temperature is usually in the range of -80°C to +150°C, preferably 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. Further, the amount of other olefin to be copolymerized with the olefin in the copolymerization is usually selected within the range of 30% by weight, particularly α6 to 15% by weight based on the olefin. The polymerization reaction using the catalyst system of the present invention is carried out in a continuous or batchwise reaction, and the conditions are less than those normally used.The copolymerization reaction may be carried out in one stage, or in two or more stages.

Effects of the Invention When the catalyst component of the present invention is used to perform homopolymerization 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 can be easily obtained, and the obtained 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.

Furthermore, in the copolymerization of ethylene and α-olefin,
A low-density copolymer with good copolymerization performance, a high bulk density, and a small amount of gold dissolved in a solvent can be easily produced with a 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 (
%) are by weight unless otherwise specified.

Specific surface area (8, A,) and pore volume (P.

V, ) and h average pore radius (M, P, R,) c, 0AR
Measurements were made using a LOKRBA 80RPTOMAT Model 01810 device. The particle size distribution of solid components and catalyst components was measured using a light transmission particle size distribution analyzer 8KN50 manufactured by Seishin Enterprises.
Measured using a Type 0 device.

Polymer melt index (M-en is A8TM
-According to D1238, temperature 190℃, load 2.16Kg
It was measured with The flow ratio (FR) is determined in the above Ml measurement at a temperature of 190°C and a load of 21. Measured at -6KQ, and the critical value (H: [, M) was measured at a temperature of 190°C and a load of 2.
The value measured at 16 kg (it is the quotient divided by M ene, represents the total outflow ratio of the polymer, and is one of the measures of the molecular weight distribution of the polymer. Also, the normal value indicates the proportion of low molecular weight polymer in the polymer) Hexane solubles (nus) is the percentage of dissolved polymer when extracted with boiling normal hexane for 95 hours in a polymer modified Soxhlet extractor.

The amount of olefin contact is determined by the amount of polymer <? ), and the amount of polymer was determined by contacting the catalyst component with a 2 N H, So4 aqueous solution and ethanol, separating the solid component from the polymer, washing the separated polymer with ethanol, and heating at 70°C.
It was determined by vacuum drying for 10 hours and weighing.

The catalyst activity Kpc is the amount of polymer produced per 12 catalyst components (
f). Solid component activity Kc is the amount (f) of polymer produced per 1 f of solid component before contact with olefin. The specific activity is the solid component 11F before contact with the olefin,
Polymerization time 1 hour, monomer partial pressure during polymerization 1Kg/cy?
The amount of polymer produced per unit (f) is shown.

Example 1 Commercially available magnesium jetoxide 85f and hexachloroethane 7q y (c2czs/Mg(OEt)z =
α45 (mole ratio) Under a nitrogen gas atmosphere, all 340 balls made of stainless steel (5US3 + 6) with a diameter of 12 mm were housed in a stainless steel ball (5US316) with an internal volume of 1 ton.
The mill pot was placed in a shaker, shaken for 15 hours to bring them into contact, and then 12 f'i of ethyl benzoate was added and shaken for 15 hours to bring them into contact. I got it.

Titanium tetrachloride treatment pulverization" + IfJ + ory2 under gas atmosphere, 300C
After adding 100 td'e of toluene and 50 td'e of titanium tetrachloride to this flask and stirring at 95°C for 2 hours, the excess liquid was removed, and 150 td'e of each solid substance was added.
Washed 6 times with 0-n-hexane at 65°C, and washed 5 times under reduced pressure.
Dry at 0℃ for 1 hour, magnesium content 1 & 2%,
A solid component (1) was obtained with a chlorine content of 5 tons and 6%, a titanium content of 5.4%, and a benzoic acid ether 1 [L1%]. This solid component has a specific surface area of 411 mVty and a pore volume of 0.27c.
c/l, average pore radius + 1.9 A.

Example 2 The order of contacting magnesium jetoxide with hexachloroethane and ethyl benzoate in Example 1 was changed to first contacting magnesium jetoxide with ethyl benzoate;
Example 1 except that the contact was then made with hexachloroethane.
Solid component (2) was obtained in the same manner as above. The composition and physical properties of this solid component were as shown in Table 1.

Example 6 A contact product of magnesium jetoxide, hexachloride, and luethane was obtained in the same manner as in Example 1.

10 g of this contact material was placed in a 600 CC flask under a total nitrogen gas atmosphere, and 100-gold toluene and 50-gold titanium tetrachloride were added thereto and stirred at 95°C for 2 hours to bring them into contact.
Excess liquid was removed. Then 150 each of the solid substances
-N-hexane at 65°C six times. Next, add ethyl benzoate Q, 3? , n-hexane and Isamt gold were added, and the mixture was stirred at 50° C. for 2 hours to bring them into contact. Thereafter, it was washed four times with each 150-hexane solution and dried at 50° C. for 1 hour under reduced pressure to obtain a solid component (3). The composition and physical properties of this solid component were as shown in Table 1.

Example 4 A contact product of magnesium jetoxide and hexachloroethane was prepared in the same manner as in Example 1 to obtain a contact product 10f'.
iPut it in a 300CC flask under a nitrogen gas atmosphere,
Add to this 100 g of toluene and 0.6 r' of ethyl benzoate.
After adding e and stirring and contacting at 65°C for 2 hours, the excess liquid was removed. Then 150 each of the solid substances
- Washed twice with toluene. Subsequently, titanium tetrachloride treatment was performed in the same manner as in Example 1 to obtain a solid component (4). The composition and physical properties of this solid component (4) were as shown in Table 1.

Example 5-8 Solid components (5) to (8)'t- were obtained in the same manner as in Example 1, except that all of the following compounds were used as electron-donating substances in place of ethyl benzoate in Example 1. The composition and physical properties of each solid component were as shown in Table 1.

Examples Electron-donating compound 5 Ethyl p-anisate 6 Methyl p-toluate 7
Di-n-butyl ether 8 Tetrahydrofuran Comparative Example 1 Magnesium jetoxide alone 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 gold substance. The composition and physical properties of this solid material were as shown in Table 1.

Comparative Example 2 In the mill pot used in Example 1, 160 g of magnesium jetoxide and 201 g of ethyl benzoate were placed and 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 obtained 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 Contact with organoaluminum compound The solid component (115f') of Example 1 was placed in a 200 cc flask under a nitrogen gas atmosphere, and 100 cc of n-hebutane was added to the solid component (115f') of Example 1.
cci was added to form a slurry. While stirring this slurry at room temperature, 6.0 mmol of triethylaluminum was gradually added dropwise over 1 hour, and stirring was continued for 2 hours after the dropwise addition. Next, the supernatant liquid was removed, washed four times with 100% n-hexane, and further dried to obtain solid component (9). The composition and physical properties of this solid component were as shown in Table 1.

Example 10 Using the solid component (7) obtained in Example 7,
Solid component α1 was obtained in the same manner as in Example 9, except that ao mmol of diethylaluminium chloride was used in place of the triethylaluminum used in Example 9. The composition and physical properties of this solid component were as shown in Table 1.

Example 11 The solid component was prepared in the same manner as in Example 9, except that 6.0 mmol of a (1:l) complex of diethylaluminium chloride and di-n-butyl ether was used instead of the triethylaluminum used in Example 9. I got ■. The composition and physical properties of this solid component were as shown in Table 1.

Example 12 The solid component (3159) obtained in Example 6 was placed in a 300 cc flask under a gas atmosphere, and 15 ml of n-hexane was added.
0cci was added to form a slurry.

While stirring the entire slurry at room temperature, 1.2 mmol of triisobutylaluminum was added dropwise over 2 hours, and the mixture was stirred for 1 hour after the dropwise addition. Subsequently, while stirring at room temperature, ethylene was introduced manually at normal pressure to obtain a solution of solid component (3) per 12 [L 5
'f of ethylene was contacted. Thereafter, the supernatant liquid was removed, washed four times with 150 tnl of n-hexane, and further dried to obtain a solid component (b). 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 solid component (3) and stem were 9.9μ and 158μ. These solid components (3) and (6) were mixed with triisobutylaluminum, an organoaluminum compound used in olefin polymerization, in the same manner as in olefin polymerization (A7/Ti = 150 (atomic ratio)) at 85°C. When brought into contact with the solid component (3), the average particle size of the solid component (3) decreases to 7.6 μ and is refined by the organoaluminum compound, but the solid component (2) changes from 1 μm to 5 μ. 1 Stainless steel (SUS
516) under a nitrogen gas atmosphere.
Catalyst components obtained in Example 1 10.1mfy triisobutylaluminum [1.7mmol and inbutane 70mfy
The temperature was raised to 80° C. to prevent polymerization. Next, is the hydrogen partial pressure t 2 h/crt? After introducing hydrogen until
Ethylene was introduced until the ethylene partial pressure became 6 to 9/l, and then 20 f of 1-butene was added. While continuously feeding ethylene gold to keep the total pressure of the polymerization system constant,
Time polymerization was performed. After the polymerization, the solvent in the polymerization system, 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 to obtain M-1.7, FR27. , bulk density 0.57 f
/cc, 181f ethylene-1-butene copolymer with true density 0.925t/cc (catalyst specific activity 5.9
60) Obtained. In addition, the n-hexane soluble portion of the polymer (nH
8) was 2.8%.

The solid components obtained in Examples 2 to 12 and Comparative Examples 1 to 2 were used in the same manner as in Application Example 1, except that the types and amounts of comonomers and hydrogen partial pressure were changed as shown in Table 2. The entire copolymerization of ethylene was carried out. The polymerization conditions and polymerization results are all shown in Table 2. In this way, when the catalyst component of the present invention is used, the catalyst activity is higher than that of the catalyst component of the comparative example.
It can be seen that the bulk density of the polymer is high, a copolymer with a lower density is produced, and the solvent-soluble portion of the copolymer is small.

Ethylene polymerization was carried out at 85° C. in the same manner as in Application Example 1, except that the solid components obtained in Examples 1.3.7 and 12 were used as all catalyst components and 1-butene was not used.

The results are shown in Table 2.

In addition, when the solid component oe treated with an organoaluminum compound and olefin is used, the average particle size of the resulting polymer is 305μ, and the proportion of fine powder polymer of 150 mesh or less is 7%, but the untreated solid component ( When 3) was used, the average particle size of the obtained polymer was 240 μm, and the fine powder polymer having 150 mesh or less was 18 μm.

Application Example 19 The solid component (1) obtained in Example 1 was added as a catalyst component to the autoclave used in Application Example 1 under a 9-gas atmosphere. Ornf, 0.7 mmol of F-lisoptylaluminium, and 70 u'ml of isobutane were charged, and the temperature of the entire polymerization system was raised to 75°C. Next, the hydrogen partial pressure is α2
After introducing frozen confectionery so that the ethylene pressure was 3 Ky/cW12,
Further, 301 liters of 1-butene was added and polymerization was carried out for 15 minutes while continuously supplying ethylene so that the total pressure of the nonapolymerization system was kept constant.

Subsequently, hydrogen was introduced so that the hydrogen partial pressure was 1-OKg/crrr2, 202 1-butene was further added, and while ethylene was continuously supplied so that the polymerization pressure was kept constant, polymerization was continued for another 60 minutes. After the polymerization is completed, the same treatment as in Application Example 1 is carried out to obtain powdered ethylene-1-butene copolymer 'i.
kl 709 (Kc15450, specific activity 4120) was obtained. The obtained copolymer was manufactured by M Engineering [1L52, FR85,
Bulk density 0.34t/cc true density 0.928
It was r/cc.

Claims (1)

[Claims] (11) Catalyst component for olefin polymerization formed by contacting magnesium alkoxide, -halogenated hydrocarbon, electron-donating compound, and titanium compound. (2) Magnesium alkoxide, halogenated hydrocarbon, and electron-donating compound A catalyst component for olefin polymerization, which is obtained by contacting a solid component obtained by contacting a titanium compound with an organoaluminum compound.