JPH03199209A - Catalyst for olefin polymerization and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst exhibiting excellent polymerization activity especially in polymerization of propylene and readily controllable of stereoregularity of generated polypropylene comprising a specific solid Ti catalyst component, an organometallic compound and an electron donor. CONSTITUTION:The aimed catalyst is composed of (A) a solid Ti catalyst component containing Mg, halogen and Ti<3+> obtained by bringing (i) activated halogen- containing Mg compound into contact with (ii) a Ti complex compound composed of titanium trichloride and an electron donor (preferably pyridine or derivative thereof) and (iii) an organometallic compound (preferably halogen- containing alkylaluminum such as diethylaluminum chloride), (B) an organometallic compound and (C) an electron donor. Besides, the component (i) is obtained by subjecting a halogen-containing Mg compound to crushing treatment. Furthermore, magnesium chloride, etc., is preferable as the halogen- containing Mg compound.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst, and more particularly, to a catalyst that exhibits high polymerization activity and particularly when propylene is polymerized. The present invention relates to an olefin polymerization catalyst and an olefin polymerization method that allow easy control of the stereoregularity of the resulting propylene polymer.

Technical Background of the Invention Titanium-based catalysts consisting of titanium compounds and organic aluminum have been known as catalysts for producing α-olefin polymers, such as polypropylene. Tactic polypropylene, syndiotactic polypropylene and atactic polypropylene are produced.

These polypropylenes with different stereoregularities are used for various purposes depending on their stereoregularity, and for this reason, it is possible to easily control the stereoregular IQ properties of the polypropylene obtained, and also to show high polymerization activity. The emergence of catalysts for olefin polymerization is still emerging.

OBJECT OF THE INVENTION The present invention has been made in view of the conventional extraction techniques as described above, and in particular, it is possible to easily control the stereoregularity of polypropylene obtained when propylene is polymerized, and it is also excellent. An olefin polymerization catalyst with a heavy content of H and a method for olefin polymerization using this olefin polymerization catalyst (JZ) is one of the main objectives.

Flight 111 of the Invention The catalyst for olefin polymerization according to the present invention comprises [A] [1] an activated halogen-containing magnesium compound, [II] titanium trichloride and electron f3t! A solid titanium catalyst component containing at least magnesium, halogen, and Ti3+ obtained by contacting the titanium complex compound and the [II1]H metal compound (a) obtained from 11) with the -j body (a), [B] It is characterized by being formed from an organometallic compound and a [C] electron donor.

In addition, the olefin polymerization method according to the present invention uses the above-mentioned olefin polymerization catalyst to produce olefins! ]!
It is characterized by polymerization or copolymerization.

In particular, when propylene is polymerized using the olefin polymerization catalyst according to the present invention, a propylene-based polymer having arbitrary stereoregularity can be produced in high yield.

DETAILED DESCRIPTION OF THE INVENTION The catalyst for olefin polymerization according to the present invention and the method for polymerizing olefin using this catalyst will be specifically described below.

In the present invention, the term "polymerization" refers not only to homopolymerization, but also to
It is sometimes used to include copolymerization, and the word polymer is sometimes used to include not only homopolymers but also polymers.

First, a flowchart diagram illustrating a process for manufacturing the olefin polymerization catalyst according to the present invention is shown.

The catalyst for olefin polymerization according to the present invention has the following components: [A] a solid titanium catalyst component; and [B] an IT metal compound metal compound;

Above, the solid catalyst component [A], such as [I] an activated halogen-containing magnesium compound, [II] a titanium complex compound obtained from titanium trichloride and an electron donor (a); , [III] (111) by contacting the metal compound (a), and contains at least magnesium, halonone, and T13+.

Examples of the method for obtaining the halokene-containing MacFuji-Ram compound which has undergone q-characterization as described in [1]〆:Q-characterization include the following methods.

(i) A method of subjecting a halogen-containing magnesium compound to pulverization treatment. The halogen-containing magnesium compound thus obtained generally has a specific surface area of 20 trr/g or more, preferably 50 rrr/g or more.

When pulverizing the halogen-containing magnesium compound, an electron donor (a) as described below may be present.

Specifically, halogen-containing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, and octoxymagnesium chloride. Alkoxymagnesium halides such as magnesium chloride; alkoxymagnesium halides such as fenoquine magnesium chloride, methylphenoxymagnesium chloride; ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Alkyl magnesium halides such as amyl magnesium chloride are used.

Among these, magnesium chloride, alkoxymagnesium chloride, and the like are particularly preferably used.

(ii) A method of preparing a magnesium complex compound from a halogen-containing magnesium compound and an electron donor, and then reacting this complex compound with an electron 90-member reactive reagent.

As the halogen-containing magnesium compound, the above-mentioned halogen-containing magnesium is used.

Moreover, as the above-mentioned electron donor, specifically, the electron Lj body (a) as described later is used.

In addition, as the electron donor reactive reagent, the electron 9 body (a
) Any compound can be used as long as it is capable of reacting with the compound, but preferred examples include organometallic compounds and halogen-containing silicon compounds as described below.

Specifically, for example, by reacting a complex of magnesium chloride and alcohol with an organometallic compound such as an organoaluminum compound or an organomagnesium compound or a halogen-containing silicon compound, the [1] activated halogen-containing magnesium Compounds can be prepared.

In addition, in the method illustrated above, a halogen-free magnesium compound can also be used as the magnesium compound. In that case, it is necessary to use the halogen-containing compound at least once in the process of preparing the [I] activated halogen-containing magnesium compound. The above-mentioned halogen-aH magnesium compounds include dialkoxymagnesiums such as jetoxymagnesium and dibutoxymagnesium, dialkylmagnesiums such as diphenoxymagnesium, dialkylmagnesiums such as diethylmagnesium and dibutylmagnesium, diallylmagnesiums such as diphenylmagnesium, and magnesium stearate. For example, magnesium salts such as

Further, as the halogen-containing compound, any compound that can halogenate the halogen-free magnesium compound can be used, and specifically, halogen-containing silicon such as silicon tetrachloride can be used. , t-
Examples include halogen-containing branched hydrocarbons such as butyl chloride, as well as acid halides.

Next, a method for preparing the titanium complex compound [II] obtained from titanium trichloride and the electron donor (a) will be explained.

Titanium trichloride is produced by reducing titanium tetrachloride by contacting it with hydrogen, metals such as metallic magnesium, metallic aluminum, metallic titanium, or any number of metallic compounds such as organomagnesium compounds, organoaluminum compounds, and organozinc compounds. The obtained titanium trichloride and the like are preferably used.

Specifically, the following compounds are used as the electron donor (a) used in preparing the titanium complex compound.

Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, hexamethylenediamine; Pyrroles such as pyrrole, methylpyrrole, dimethylpyrrole; Pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethyl Nitrogen-containing cyclic compounds such as pyridines such as pyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride; piperidines; quinolines; isoquinolines;

Among these, nitrogen-containing cyclic compounds are preferred, and pyridine and its derivatives are particularly preferred.

Cyclic oxygen-containing compounds such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, ditedropyran.

Carbon number of methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isobu-avir alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. 1 to 18 alcohols; Phenols with 6 to 20 carbon atoms that may have an f-class alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; acetone; Methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylace I
Ketones with 3 to 15 carbon atoms, such as benzoquinone; Aldehydes with 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, henzaldehyde, tolualdehyde, naphthaldehyde; Methyl formate, methyl acetate, ethyl acetate , vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate,!・Methyl toluate, ethyl toluate, amyl toluate,
Ethyl ethyl benzoate, methyl anisate, maleic acid n
-butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone , δ−
Organic acid esters having 2 to 30 carbon atoms, such as valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride, penzoilc. Acid halides having 2 to 15 carbon atoms such as toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether epoxy-p-
Ethers and diethers having 2 to 20 carbon atoms such as menthane; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Methylamine, ethylamine, diethylamine, tributylamine, piperidine, l-ribenzylamine, aniline , pyridine, picoline, tetramethylene diamine, and other nitriles; acetonitrile, benzonitrile, tolnitrile, and other nitriles; acetic anhydride, phthalic anhydride, benzoic anhydride, and other acid anhydrides.

Further, as the electron N-form (a), the following general formula [I
It is also possible to use organosilicon compounds represented by a].

, RSI(OR') 4-n-CIa [wherein R and R' are hydrocarbon groups, and 0xn<4] An organic compound represented by the above general formula [Ia] Specifically, the silicon compound includes trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldie!・Xysilane, diisopropyldimethoxysilane, L-butylmethyldimethoxysilane, t-
Butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis0-)lyldimethoxysilane, bism-t-zyldimethoxysilane, bisp-)lyl dimethquinsilane,
bis I)-) lyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilanemethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,
Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyl] ethoxysilane, ethyl!・Lietquinsilane, vinyltriethoxysilane, t
-Butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltrie!・Xysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxyrane, cyclohexyltrimethoxyrane, 2-norbornanetrimethoxysilane, 2
- norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane,
Dimethyltetraethoxydisiloxane and the like are used.

Furthermore, as the electron N-body (a), the following general formula [
IIa] can also be used.

[Wherein, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R3 is a hydrocarbon group, m is O≦m≦2. ] In the above formula [IIa], Ri is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include, in addition to the cyclopentyl group, cyclopentyl groups having an alkyl group such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl M, and 2,3-dimethylcyclopentyl group.

In the formula [IIa, R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group exemplified as R1 and a cyclopentyl group having an alkyl group can be similarly mentioned.

Further, in the formula [[1a], R3 is a hydrocarbon group, and examples of R3 include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Specific examples of such a silicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane.

Synclopentyldimethoxysilane, bis(2-methyltonclopentyl)dimethoxysilane, bis(2,3-
Dialkoxysilanes such as dimethylcyclopentyl)dimethoxysilane and dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane , cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, and other monoalkoxysilanes. Among these electron donors, nitrogen-containing cyclic compounds are preferred;
Particularly preferred are pyridine and pyridine derivatives.

The amount of electron donor (a) used in preparing the titanium complex compound as described above is at least 0.5 mol or more, preferably 1 mol or more, particularly preferably 2 to 5 mol, per 1 mol of titanium trichloride. be. There is no particular upper limit on the amount of electron donor used, but from an economic standpoint titanium trichloride 1
The amount is preferably 1000 mol or less, more preferably 100 mol or less, particularly preferably 10 mol or less.

Further, the contact between titanium trichloride and electron 11 (a) is preferably carried out at a temperature of usually -100 to 300°C, preferably -50 to 100°C.

The above reaction is based on the electron [%! The -i form (a) may be used as a solvent, but it is generally preferable to use an inert hydrocarbon solvent as described below.

Further, a complex obtained from titanium trichloride and electron 9 (a) is generally titanium trichloride and electron J'j.

In the form of a body composition, 9 electron atoms per mole of titanium trichloride are usually 7:'+ 1 to 10 moles, preferably 2 to 5 moles.
The composition is particularly preferably 2.5 to 4 moles.

As the organometallic compound [m], group 1 to group Ⅰ of the periodic table are used.
Organometallic compounds of group metals are used, and specifically, the following compounds are used.

(In the formula, R and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. X represents a halogen atom, and 0<m ≦3, n is a number of 0≦n<3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q-3).

(ii) A complex alkylated product of Group 1 metal and aluminum represented by M AgR'4 (wherein M is Li or Na, and R1 is the same as above).

(iii) R’ R2Mg (In the formula, R1 and R2 are the same as above).

Mg is Mg, Zn or Cd)
Dialkyl compounds of group or group II.

Examples of the organic aluminum compounds belonging to (i) above include the following compounds.

- Formation R1□Ag (OR2) -m (wherein R and R2 are the same as above. m is preferably 1
, 5≦m≦3), ■ General formula RAgX31 (wherein R1 is the same as above, X is halogen, m is preferably 0<m<3), - formation R1□A D Hsl (In the formula, R1 is the same as above. m is preferably 2≦m<3
), (wherein R1 and R2 are the same as above. X is halogen,
0<m≦3, Q5r1<3.0≦q<3, m+ n+
q-3) can be halved.

More specifically, aluminum compounds belonging to (1) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum such as diethylaluminum ethoxide and diethylaluminum ethoxide. Alkoxide: Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, aluminum sesquibutoxide, partially alkoxylated alkylaal miniram diethyl having an average 0,5 homogeneous composition represented by R122,5All (OR), etc. Dialkylaluminum halides such as aluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; Ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dichloride; Partially halogenated alkyl aluminum hydrides such as alkyl aluminum cybarides such as bromide; dialkyl aluminum hydrides such as diethylaluminum hydride and dibutyl aluminum hydride; alkyl aluminum dihydrides such as ethyl aluminum dicdride and probylaluminum dihydride; and other partially hydrogenated alkylaluminums, such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, etc., and other partially alkoxylated and halokenated alkylaluminums.

Examples of compounds similar to (i) include a-type aluminum compounds in which two or more aluminum atoms are fed via oxygen atoms or nitrogen atoms. Something like this ^
For example, (CH) Ag0AD (C2
H5) 2, 52 (CH) ANOAN ('C4H9), 2,
92 2 H5 Methylaluminoxane can be mentioned.

Examples of compounds belonging to the above (11) include LI Ag (
Examples include C2H5)4, Li AN (C7H15)4, and the like.

Among these, organoaluminum compounds are preferably used, and halogen-containing alkyl aluminums are particularly preferably used.

The organometallic compound [III] and the titanium complex compound [U] are used in amounts such that the AX)/Ti (atomic ratio) is usually 1 to 1,000, preferably 2 to 100, particularly preferably 3 to 10. is desirable.

By bringing the cN-activated halogen-containing magnesium compound prepared as described above, [■] titanium complex compound and [III] organometallic compound into contact with each other,
A solid titanium catalyst component [A] containing at least magnesium, l\logen, and Ti3+ is obtained.

activated halogen-containing magnesium compound [I],
Titanium trichloride complex compound [II] and organometallic compound [
In contact with the titanium complex compound [III], the titanium complex compound [
II] and the activated norogen-containing magnesium compound [1] have a Ti/Msr (atomic ratio) of 0.000.
It is desirable to use an amount such that the amount is 0.01 to 0.1.

In addition, it is preferable to carry out the contact with an inert hydrocarbon solvent as described below.

In such a solid titanium catalyst component [A], the halogen/titanium (atomic ratio) is 5 to 5000, preferably 10 to 2.
000, and the magnesium/titanium (atomic ratio) is 5~
It is desirable that it is 100,000, preferably 10 to 5,000.

This solid titanium catalyst component [A] contains magnesium halide with a smaller crystal size than commercially available magnesium halide, and its specific surface area is approximately 20
rrr/g or more, preferably about 50 to 1000 bo/g,
More preferably about 80-500 rrr/g. In this solid titanium catalyst component [A], the above components are combined to form 11 and 2 catalyst components, so
Washing with hexane does not change the quality of the i11.

Next, [
To explain the organometallic compound [B], this G machine metal compound [B] includes the organometallic compound [I
II] is used.

Also used in the olefin polymerization catalyst according to the present invention [
C] To explain the electron donor, this electron donor [
As C], the same one as the electron q body (a) described above is used.

In the present invention, the solid titanium catalyst component [A] as described above is used.
, an olefin polymerization catalyst consisting of an organometallic compound [B] and an electron donor [C] is used to polymerize an olefin. At this time, it is preferable to prepolymerize an α-olefin in the olefin polymerization catalyst. . This prepolymerization is carried out at 0.1 to 500 g per 1 g of catalyst for olefin polymerization, preferably from 0.3 to 300+; r, particularly preferably from 1 to 1
This is carried out by prepolymerizing the α-olefin in an amount of 0.00 g.

In the prepolymerization, a catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization.

The concentration of the solid titanium catalyst component [A] in the prepolymerization is usually 0.01 to 200 mmol, preferably about 0.00 mmol, in terms of titanium atoms, per 1 g of the inert hydrocarbon medium described below. ] to 100 mmol, particularly preferably 1 to 50 mmol.

The amount of H metal compound [B] is determined by the amount of solid titanium catalyst component [
0.1 to 500 g per 1 g of A1, preferably 0.3 to 30
It is sufficient to have all the components so that 0 g of polymer is produced, and usually about 0.1 to 100 mol, preferably about 0.5 to 50 mol, especially about 0.1 to 100 mol, particularly The amount is preferably 1 to 20 moles.

Electron (co-17 body [C] is a solid titanium catalyst component [A]
It is preferably used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 10 mol, per mol of titanium atoms therein.

The T-prepolymerization is preferably carried out under mild conditions by adding the olefin and the catalyst components described above to an inert hydrocarbon medium.

Examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Examples include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Incidentally, the prepolymerization can be carried out using the olefin itself as a solvent, or the prepolymerization can be carried out substantially in the absence of a solvent.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, and specifically, propylene is preferably used.

The reaction temperature during prepolymerization is usually about -20 to +100°C.
, preferably about -20 to +80°C, more preferably 0
It is desirable that the temperature is in the range of ~+40°C.

In addition, in prepolymerization, molecules such as hydrogen m:J
L+ moderators can also be used. Such a molecular weight regulator has an intrinsic viscosity [η] of about 0.2 dN/g of the polymer obtained by prepolymerization measured in decalin at 135°C.
As mentioned above, it is desirable to use the amount preferably in the range of about 0.5 to 10 dN/g.

The T-(Q polymerization is carried out, as described above, using a solid titanium catalyst component [approximately 0.1 to 500 g, preferably approximately 0.3 to 300, particularly preferably 1 to 10 (] g per Ar1.pr).
It is desirable to carry out the process in such a way that a polymer of If the amount of senryo polymerized is too large, the production efficiency of the olefin polymer may decrease.

The prepolymerization can be carried out in a quarter-part manner or in a continuous manner.

Olefins that can be used in this polymerization include ethylene, propylene, l-butene, 4-methyl-
Examples include olefins having 2 to 20 carbon atoms such as 1-pentene and tooctene. In the polymerization method of the present invention, these olefins can be used alone or in combination.

In addition, when copolymerizing these olefins, compounds having polyunsaturated bonds such as conjugated dienes and non-conjugated dienes can also be used as polymerization raw materials.

In the polymerization method of the present invention, the main polymerization of olefin is usually carried out in a gas phase or a liquid phase.

When the main polymerization takes the reaction form of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, or an olefin in the shape of a lug at the reaction temperature can be used.

In the polymerization method of the present invention, the solid titanium catalyst component [
A] is usually about 0.001 to 0.5 mmol, preferably about 0.00 mmol in terms of Ti atoms per 1 g of polymerization volume.
It is used in amounts of 5 to 0.1 mmol. In addition, the organometallic compound [B] usually contains about 1 to 2000 metal atoms per mole of titanium atoms in the prepolymerization catalyst component in the polymerization system.
The amount used is mole, preferably about 5 to 500 moles. Furthermore, the electron donor [C] is usually about 0,0 per mole of metal atom in the organometallic compound [B].
0.01 to 10 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.05 to 1 mol.

If hydrogen is used in the main polymerization Hj;, the molecular weight of the resulting polymer can be adjusted, and a polymer with a large melt flow rate i can be obtained.

In the present invention, the polymerization temperature of the olefin is generally 1+
4. , about 20~200℃, preferably about 50~] 00
'C, the pressure is 7:'+,';:'r°pressure~1-
00 kg/cn? , (lr preferably about 2 to 50 k
g/cn? is set to In the polymerization of the present invention), the polymerization can be carried out in any of the four-part, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In this way? The polymer of 11 olefins is li
(t) A self-polymer (can be either a polymer or a block copolymer).

When olefin polymerization, particularly propylene polymerization, is carried out using the above catalyst for olefin polymerization, the isotactic index (I
I) A propylene polymer having a content of 10% or more, preferably 30% or more, particularly preferably 50% or more is obtained. At this time, by adjusting the amount of electron 9% donor [C],
Stereoscopicity can be easily controlled.

In addition, in the present invention, since the yield of polymer per olefin polymerization catalyst is high, there is little catalyst residue in the polymer, and therefore, even if the operation of removing the catalyst from the polymer is omitted, the coloring caused by the catalyst will not occur. A white olefin polymer is obtained.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 3 [Preparation of solid catalyst component [A]] 30 g of anhydrous magnesium chloride and 50 stainless steel poles with a diameter of 25 mm were added to a stainless steel pot having an internal volume of 1 g under a nitrogen atmosphere, and the mixture was heated at room temperature for 48 hours. An activated halogen-containing rr magnesium compound [1] was prepared by shaking and pulverizing magnesium chloride. This halokene-containing magnesium compound [I]
The specific surface area was 97 bo/g.

Meanwhile, 4.3 g of titanium trichloride was added to 40 ml of purified n-hebutane.
Add 10 ml of distilled pyridine to the suspension, and stir at room temperature for 16 hours. After mixing, the titanium trichloride/pyridine complex was prepared by placing the reacted pyridine and the solvent in a vacuum seedling pot.

15 g of the pulverized magnesium chloride and 54 g of the titanium trichloride/pyridine complex were suspended in purified heptane and stirred to give 15 mmol...'! 1 mole of ethylaluminum sesquichloride in j/l of hebutane in D
The mixture was stirred at room temperature for 16 hours.

? The solid catalyst component can be removed by thoroughly washing the purified solid material with heptane. 11.

The titanium atom content in the solid catalyst component was 0.043% by weight.

[Polymerization of propylene] 100 ml of purified n-hebutane was added to a 200 ml glass flask equipped with a stirrer, followed by 250 mg of solid catalyst component [A] and further the amounts of ethyl benzoate listed in the table. After the addition, propylene was fed and the polymerization was then initiated by adding 1 mmol of triethylaluminum. Polymerization was carried out at 40°C for 1 hour, and was stopped by adding a mixture of methanol (ethanol containing a small amount of hydrochloric acid) and hydrochloric acid into the polymerization vessel.

The polymerization results are shown in Table-1.

Table-1 No. Addition amount (mmol) kg-907g-Ti1
0, 1 5. 002
0, 2 3. 763 0.4
3. ], 1* I■ Boiling helibutane extraction residual rate 6 73, 0 84, 6 94, 4 4,

[Brief explanation of drawings]

Soco Figure 1 is Olefin according to the present invention catalyst for polymerization (component) It is a flowchart figure showing the preparation process of. Teenager ■14! Man

Claims (2)

[Claims] (1) [A] [I] An activated halogen-containing magnesium compound, [II] a titanium complex compound obtained from titanium trichloride and an electron donor (a), and [III] an organometallic compound (a), A catalyst for olefin polymerization formed from a solid titanium catalyst component containing at least magnesium, halogen, and Ti^3^+ obtained by bringing them into contact with each other, [B] an organometallic compound, and [C] an electron donor. (2) A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst according to claim 1.