JPH04168109A - Catalyst for olefin polymerization and polymerization of olefin - Google Patents

Abstract

PURPOSE:To readily control stereoregularity and to polymerize an olefin by using a highly active catalyst comprising a solid titanium catalytic component prepared by bringing a specific Ti complex compound into contact with a halogen-containing Mg compound and an organometallic compound, an organometallic compound and an electron donor. CONSTITUTION:An olefin (e.g. propylene) is polymerized or copolymerized in the presence of a catalyst comprising (A) a solid titanium catalytic component containing at least magnesium, a halogen and trivalent titanium, having >0.5wt.% titanium content, prepared by bringing a titanium complex compound obtained from titanium trichloride and an electron donor (e.g. pyridine) into contact with a halogen-containing magnesium compound (e.g. magnesium chloride) and an organometallic compound (e.g. ethylaluminum sesquichloride), (B) an organometallic compound (e.g. trimethylaluminum) and optionally (C) an electron donor (e.g. methyl benzoate).

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 a catalyst for reflex polymerization and a method for polymerizing olefins, which allow the stereoregularity of the resulting propylene polymer to be easily controlled.

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. Therefore, it is possible to easily control the stereoregularity of the resulting polypropylene and to develop a reflex resin that exhibits high polymerization activity. The emergence of polymerization catalysts is desired.

JP-A No. 64-16806 discloses a catalyst for producing atactic PP having a relatively high molecular weight.
There was a problem that the activity per weight of catalyst was low.

As a result of research to improve the above problems, the present inventors found that
A catalyst with higher activity than conventional catalysts was discovered and the present invention was completed.

OBJECTS OF THE INVENTION The present invention has been made in view of the prior art as described above, and in particular, it is possible to easily control the stereoregularity of polypropylene obtained by polymerizing propylene, and to provide an excellent method. It is an object of the present invention to provide a method for polymerizing olefins using an olefin polymerization catalyst and a double reflex polymerization catalyst having polymerization activity.

Summary of the Invention The olefin polymerization catalyst according to the present invention comprises [8] [I
II] A titanium complex compound obtained from titanium trichloride and an electron donor (a), [III] A halogen-containing magnesium compound, and [III] an organometallic compound obtained by contacting at least magnesium, halogen, and trivalent titanium. A solid titanium catalyst component containing more than 0.5% by weight of titanium, [B] an organometallic compound, and optionally [C] an electron donor. It is characterized by

Further, the method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized or copolymerized using the above-mentioned catalyst for reflex polymerization.

In particular, when propylene is polymerized using the olefin polymerization catalyst of the present invention, a propylene 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 term polymer is sometimes used to include not only homopolymers but also copolymers.

FIG. 1 shows an explanatory diagram of the preparation process of the olefin polymerization catalyst according to the present invention.

The olefin polymerization catalyst according to the present invention is formed from [A] a solid titanium catalyst component, [B] an organometallic compound, and optionally [C] an electron donor.

The solid titanium catalyst component [A] as described above is [III
] A titanium complex compound obtained from titanium trichloride and an electron donor (a), [II] a halogen-containing magnesium compound, and [III
] Obtained by contacting with an organometallic compound, it contains at least magnesium, halogen, and trivalent titanium, and the titanium content exceeds 0.5% by weight. Furthermore, this solid titanium catalyst component [A] may contain an electron donor as necessary.

A method for preparing the titanium complex compound [III] obtained from titanium trichloride and the electron donor (a) used in the present invention will be explained.

Titanium trichloride is produced by reducing titanium tetrachloride by contacting it with hydrogen, metals such as metallic magnesium, metallic aluminum, and metallic titanium, or organometallic compounds such as organomagnesium compounds, organoaluminum compounds, and organozinc compounds. Titanium trichloride obtained by the above method is preferably used.

As the electron donor (a) used in preparing the titanium complex compound [III], specifically, the following compounds are used.

Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine; Viroles such as pyrrole, methylpyrrole, dimethylvirol; pyrroline; pyrrolidine; indole ; Pyridines such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride; Nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines, etc. : Tetrahydrofuran, 1,4-cineole, 1. Cyclic oxygenated compounds such as cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalan, tetrahydropyran, pyran, ditedropyran; methanol, ethanol, propatool, pentanol, hexanol, octatool, 2 - Alcohols having 1 to 18 carbon atoms such as ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol: acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, acetylacetone, benzoquinone, etc. Ketones having 3 to 15 carbon atoms; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, acetic acid Propyl, 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 ethylbenzoate, methyl anisate, n-maleate
Butyl, diisobutyl methylmalonate, di-n-hexylnadic cyclohexenecarboxylate, diethyl 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 ethyl carbonate; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, and anisyl chloride: Methyl ether , ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether Ethers having 2 to 20 carbon atoms such as epoxy-p-menthane; 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2- Isobutyl-1,3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobenthyl.

3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxy Propane, 2,2-dicyclopentyl-1,3
-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo-[2,2,11-heptane, diphenyldimethoxymethylsilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, Diethers such as 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Nitriles such as acetonitrile, benzonitrile, and tolnitrile; Acetic anhydride Acid anhydrides such as , phthalic anhydride, and benzoic anhydride are used.

Further, as the electron donor (a), the following general formula [I
Organosilicon compounds represented by a] can also be used.

R,5i(OR')4-n-[Iaco[wherein R and R' are hydrocarbon groups, 0kn<4
Specifically, the organosilicon compound represented by the general formula [Ia] as described above includes trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, t- Butylmethyldimethoxysilane, t-
Butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis o-tolyldimethoxysilane, bis m-)lyldimethoxysilane, bis p-)lyldimethoxysilane , bis p-)lyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, hinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane Silane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane , 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(
β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

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

SIR'R21= (OR")s-...[I[a][
In the formula, 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, R3 is a hydrocarbon group, and m is 0≦m≦2. ] In the above formula [I[a], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include cyclopentyl groups having alkyl groups such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group in addition to cyclopentyl group.

Further, in formula [I[a], 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.

Further, in formula [I[a], 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.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, nitricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane Examples include monoalkoxysilanes such as silane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

As these electron donors (a), nitrogen-containing cyclic compounds are preferred, and pyridine and pyridine derivatives are particularly preferred.

Electron donor (a) used in preparing a titanium complex compound from the above electron donor (a) and titanium trichloride
) is at least 0.0% per mole of titanium trichloride.
5 moles or more, preferably 1 mole or more, particularly preferably 2 moles
~5 moles. Is there any particular upper limit to the amount of electron donor (a) used? Considering economic efficiency, it is preferably 1000 mol or less, more preferably 10 mol or less, per 1 mol of titanium trichloride.
It is 0 mol or less, particularly preferably 10 mol or less.

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

Although the above reaction may be carried out using the electron donor (a) as a solvent, it is generally preferable to carry out the reaction using an inert hydrocarbon solvent as described below.

Further, the complex obtained from titanium trichloride and an electron donor (a) is generally in the form of a composition of titanium trichloride and an electron donor, and the amount of electron donor (a) is usually 1 mole of titanium trichloride. ~10 mol, preferably 2 to 5 mol, particularly preferably 2
．． The composition is 5 to 4 moles.

In the present invention, the halogen-containing magnesium compound [II] used in the preparation of the solid titanium catalyst component [A] specifically includes halogenated magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, etc. Magnesium; Alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; Alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Magnesium amyl chloride and alkyl magnesium halides are used.

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

Such a halogen-containing magnesium compound [II] can be activated and used, for example, by the following method.

(1) A method of pulverizing a halogen-containing magnesium compound. The magnesium compound thus obtained has a specific surface area of generally 20rd/g or more, preferably 5.
It is 0rrf/g or more.

When subjecting the magnesium compound to pulverization treatment, an electron donor (b') may be present. This electron donor (b
) can be the electron donor (a) described above.

(2) Halogen-containing magnesium compound and electron donor (
A method of preparing a magnesium complex compound from b) and then reacting this complex compound with an electron donor-reactive reagent.

As the electron donor (b), specifically, the compounds mentioned above as the electron donor (a) are used, preferably alcohols having 1 to 18 carbon atoms, particularly preferably ethanol, butanol, 2 - Ethylhexanol is used.

Further, as the electron donor-reactive reagent, the electron donor (b
) 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, the halogen-containing magnesium compound [I[] is activated 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. I can do it.

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 activating the halogen-containing magnesium compound [I[]. The above-mentioned halogen-free 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. Examples include magnesium salts such as

Further, as the halogen-containing compound, any compound can be used as long as it is capable of halogenating the halogen-free magnesium compound, and specifically, halogen-containing silicon compounds such as silicon tetrachloride, t
In addition to halogen-containing branched hydrocarbons such as -butyl chloride, acid halides and the like can be exemplified.

As a specific method, a method for obtaining an activated halogen-containing magnesium compound by bringing butylethylmagnesium and silicon tetrachloride into contact and reacting can be exemplified.

Another method for obtaining an activated halogen-containing magnesium compound is to contact and react an organomagnesium compound such as a Grignard reagent with an electron donor (d), and if necessary, further contact with a halogen-containing compound. Is there a way to do it?

As the electron donor (d) to be brought into contact with and reacted with the organomagnesium compound, those similar to the electron donor (a) may be used, or among them, organic acid esters having 2 to 30 carbon atoms are preferably used. In addition to the halogen-containing silicon compounds, halogen-containing branched hydrocarbons, and acid halides, halogen-containing compounds such as 1.1.1-trichloroethanol can be used as halogen-containing compounds if necessary. The alcohol contained may be exemplified.

As a specific method, butylmagnesium chloride and ethyl orthoformate are brought into contact and reacted, and then 1, 1. i A method for obtaining an activated halogen-containing magnesium compound by further contacting with trichloroethanol can be exemplified.

In the present invention, as the organometallic compound [I [III] used in the preparation of the solid titanium catalyst component [A], an organometallic compound of a metal from Group 1 to Group II of the periodic table is used, and specifically, The following compounds are used.

(1) R', AI (OR2), H, X.

(In the formula, R1 and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, 0<m≦3, n is 0≦n<3, p is 0≦p<3, q
is a number of 0≦q<3, and m±n+p+q=3
An organoaluminum compound represented by

(2) M'A IR'.

(In the formula, Ml is Li, Na, or R1, and R1 is the same as above.) A complex alkylated product of a Group 1 metal and aluminum.

(3) R’R2M2 (In the formula, R1 and R2 are the same as above.

M2 is Mg, Zn or Cd)
Dialkyl compounds of group or group II.

Examples of the organoaluminum compounds that belong to the above (1) include the following compounds.

General formula R', A I (OR2) 5-1 (wherein, R1
and R2 are the same as above. m is preferably 1.5≦m≦
3), general formula R', A IX 3-+++ (wherein R1 is the same as above, X is halogen, m is preferably 0<m<3), general formula R1YA IH ,-.

(In the formula, R1 is the same as above. m is preferably 2≦m<3
), general formula R', Al (OR2) , , X.

(In the formula, R1 and R2 are the same as above. X is halogen,
0<m≦3.0≦n<3.0≦q<3, m+n+q=
3) can be mentioned.

More specifically, the aluminum compounds belonging to (1) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide. : Alkylaluminium sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R1□sA 1 (OR2). , 5, etc. Dialkyl aluminum halides such as diethylaluminium chloride, dibutyl aluminum chloride, diethylaluminium bromide: ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum Alkylaluminum sesquihalides such as sesquipromide; partially halogenated alkyl aluminum such as alkyl aluminum cybarides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; dialkyls such as diethylaluminum hydride, dibutyl aluminum hydride Aluminum hydride: Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, probylaluminum dihydride; etc. Partially alkoxylated and halogenated alkyl aluminums may be mentioned.

Compounds similar to (1) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2H6)2AIOAl (C
2H6)2, (C4H9)2AIOAl (C4H,)
2, (C2H5)2AINAl (C2H5)2C2H
.

Examples include methylaluminoxane.

Examples of compounds belonging to the above (2) include LiAt (C2H6) 4 and LiAl (C7H+s) 4.

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

Such an organometallic compound [I[] may be used in contact with the electron donor (b) as described above, if necessary.

The organometallic compound [In] and the titanium complex compound [III] as described above have an Al/Ti (atomic ratio) of usually 1 to 50.
00 preferably 2-3000 particularly preferably 3-100
It is desirable to use the amount such that the amount becomes 0.

Contact of the above compound is carried out at -80 to 200°C1, preferably -
50-100°C, more preferably -30-50°C
It is carried out under the following conditions.

Further, the contact is preferably carried out in the presence of an inert hydrocarbon solvent, which will be described later.

As long as the above-mentioned three types of compounds are contacted at the same time,
The contact method is arbitrary, but for example, (1) a method of simultaneously adding the titanium trichloride complex compound [II] and the organometallic compound [III] to the halogen-containing magnesium compound [II]; (2) a method of adding the titanium trichloride complex compound [II] simultaneously; [Method of simultaneously adding halogen-containing magnesium compound [II] and organometallic compound [I[] to II, (3) Adding titanium trichloride complex compound [II and halogen-containing magnesium compound [II] to organometallic compound [111[]]
], (4) a method in which a titanium trichloride complex compound [II], a halogen-containing magnesium compound [II], and an organometallic compound [I] are simultaneously added to a reactor.
(5) Adding titanium trichloride complex compound [I] to halogen-containing magnesium compound [II] at the same time.
(6) Adding organometallic compound [I[] to halogen-containing magnesium compound [II] and then contacting titanium trichloride complex compound [II] , (7) Titanium trichloride complex compound [organometallic compound [II]
For example, a method of adding II and then contacting with a magnesium compound containing No. 10 gene can be exemplified.

[III] Titanium complex compound obtained from titanium trichloride and electron donor (a) prepared as described above, [I
A solid titanium catalyst component [AI] is obtained by contacting the magnesium compound containing I] II and the organometallic compound [III]. In this contact, an electron donor (e) may be present together if necessary. As this electron donor (e), the above-mentioned electron donor (a) can be used.

As described above, at least magnesium, halogen and trivalent titanium, and optionally an electron donor (e
) containing a solid titanium catalyst component [AI is obtained.

In contacting the trivalent titanium complex compound [II], the halogen-containing magnesium compound [II], and the organometallic compound [III], the trivalent titanium complex compound [II] and the halogen-containing magnesium compound [II] /
It is desirable to use an amount such that magnesium (atomic ratio) is 0.01 to 100, preferably 0.015 to 5o.

Further, in the contact, it is preferable to carry out the contact in the presence of an inert hydrocarbon solvent, which will be described later.

Such a solid titanium catalyst component [In AI, halogen/trivalent titanium (atomic ratio) is 3 to 200, preferably 3 to 1
50, and magnesium/trivalent titanium (atomic ratio) is 0.
．． 01-100, preferably 0.02-70.

The solid titanium catalyst component [A
The amount of trivalent titanium supported in I exceeds 0.5% by weight.

This solid titanium catalyst component [AI contains magnesium halide with a smaller crystal size compared to commercially available magnesium halides, and usually has a specific surface area of about 20 r.
rr/g or more, preferably about 50 to 1000rd/g,
More preferably, it is about 80 to 500 IIf/g. Since this solid titanium catalyst component [AI] is integrated with the above components to form the catalyst component, its composition does not substantially change by hexane washing.

Next, [
B] Organometallic compounds will be explained.

As such an organometallic compound [B], a compound similar to the above-mentioned organometallic compound [II] is used. Furthermore, metallocene compounds as shown below can also be used.

The metallocene compound used in the present invention is an organic transition metal compound containing a ligand having a cyclopentadienyl skeleton, and is represented by the following formula.

Lx (where M is a transition metal, L is a ligand that coordinates to the transition metal, X is a coordination number, and at least one L
are ligands and substituents that have a cyclopentadienyl skeleton, and there are few ligands that have a cyclopentagenyl skeleton, and these ligands that have a cyclopentagenyl skeleton are alkylene groups, substituted alkylene groups, silylene groups. or a substituted silylene group, and the ligand other than the one having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
12 hydrocarbon groups, alkoxy groups, monoloxy groups, halogens, or hydrogen. ) Examples of the ligand having a cyclopentagenyl skeleton include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, an n-butylcyclopentagenyl group,
Examples include alkyl-substituted cyclopentagenyl groups such as dimethylcyclopentagenyl group and pentamethylcyclopentagenyl group.

The ligand having a cyclopentadienyl skeleton as described above may be coordinated to two or more other transition metals,
In this case, the ligands having at least two cyclopentadienyl skeletons may be bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. Examples of the alkylene group include a methylene group, ethylene group, and propylene group. Examples of the substituted alkylene group include an isopropylidene group. Examples of the substituted silylene group include a dimethylsilylene group and a diphenylsilylene group.

The ligand other than the ligand having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group; aryl groups include phenyl group, tolyl group; and aralkyl groups include benzyl group, Examples include neophyll groups.

Examples of the alkoxy group include a methoxy group, nidoxy group, and butoxy group, and examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Among such metallocene compounds, titanocene compounds include bis(cyclopentagenyl) titanium monochloride monohydride, bis(cyclopentagenyl) titanium monopromide monohydride, and bis(cyclopentagenyl) titanium monopromide monohydride. ) methyltitanium hydride, bis(cyclopentagenyl)ethyltitanium hydride, bis(cyclopentagenyl)phenyltitanium hydride, bis(cyclopentagenyl)benzyltitanium hydride, bis(cyclopentagenyl)neopentyltitanium hydride , Bis(methylcyclopentagenyl)titanium monochloride hydride, Bis(indenyl)titanium monochloride monohydride, Bis(cyclopentagenyl)titanium dichloride, Bis(cyclopentagenyl)titanium dibromide, Bis(cyclopentagenyl)titanium dibromide. Bis(cyclopentagenyl)methyltitanium monochloride, Bis(cyclopentagenyl)ethyltitanium monochloride, Bis(cyclopentagenyl)cyclohexyltitanium monochloride, Bis(cyclopentagenyl)phenyltitanium monochloride, Bis(cyclopentagenyl) ethyltitanium monochloride ) benzyl titaniram monochloride, bis(methylcyclopentadienyl) titanium dichloride, bis(dimethylcyclopentajenyl) titanium dichloride, bis(n-butylcyclopentajenyl) titanium dichloride bis(indenyl) titanium dichloride, bis( indenyl) titanium dibromide, bis(cyclopentagenyl) titanium dimethyl, bis(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium dibenzyl, bis(cyclopentagenyl) titanium methoxychloride, bis( cyclopentagenyl) titanium ethoxy chloride, bis(methylcyclopentagenyl) titanium ethoxy chloride, bis(cyclopentagenyl) titanium phenoxy chloride, bis(fluorenyl) titanium dichloride, ethylene bis(indenyl) dimethyl titanium, ethylene bis( indenyl) diethyl titanium, ethylenebis(indenyl)diphenyltitanium monochloride, ethylenebis(indenyl)methyltitanium monochloride, ethylenebis(indenyl)ethyltitanium monochloride, ethylenebis(indenyl)methyltitanium monopromide, ethylenebis(indenyl)methyltitanium monochloride ) titanium dimethyl do, ethylenebis(indenyl)titaniumdimethyldo, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethyltitanium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl) ) Methyl titanium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)
Titanium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium dibromide, ethylenebis(4-methyl-1-indenyl)titanium dichloride, ethylenebis(5-methyl-1-indenyl)titanium Dichloride, Ethylenebis(6-methyl-1-indenyl)titanium dichloride, Ethylenebis(7-methyl-1-indenyl)titanium dichloride, Ethylenebis(5-methoxy-1-indenyl)titanium dichloride, Ethylenebis(2,3 -dimethyl-1-indenyl) titanium dichloride, ethylenebis(4,7-simethyl-1-indenyl)titanium dichloride, ethylenebis(4,7-simethoxy-1-indenyl) titanium dichloride, dimethylsilylenebis(cyclopentagenyl) titanium Dichloride, Dimethylsilylenebis(indenyl)titanium dichloride, Dimethylsilylenebis(methylcyclopentagenyl)
Examples include titanium dichloride, isopropylidene bis(indenyl) titanium dichloride, and isopropylidene (cyclopentagenylfluorenyl) titanium dichloride.

Above, a specific example in which the transition metal (M) is titanium has been described, but as this transition metal (M), besides titanium, Z
An example is r5Hf.

Further, to explain the [C] electron donor (C) used as necessary in the olefin polymerization catalyst according to the present invention, the electron donor (C) includes the above-mentioned electron donor (a). A similar one may be used, preferably having 2 or more carbon atoms.
30 organic acid esters, more preferably aromatic organic acid esters, particularly preferably ethyl benzoate, methyl toluate, etc. are used.

In the present invention, the solid titanium catalyst component [A] as described above is used.
Olefin polymerization is carried out using an olefin polymerization catalyst consisting of an organometallic compound [B] and an olefin polymerization catalyst to which an electron donor [C] is added if necessary. It is preferable to prepolymerize the α-olefin. This prepolymerization is carried out at 0.1 to 500 g, preferably 0.1 to 500 g, per 1 g of olefin polymerization catalyst.
α in an amount of 3 to 300 g, particularly preferably 1 to 100 g
- carried out by prepolymerizing the olefin.

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 about 0.01 to 200 mmol, preferably about 1 to 100 mmol, particularly preferably about 1 to 100 mmol, in terms of titanium atoms, per inert hydrocarbon medium if described below. A range of 1 to 50 mmol is desirable.

The amount of organometallic compound [B] is determined by the amount of solid titanium catalyst component [
A] 0.1 to 500 g per Ig, preferably 0.3 to 3
The amount may be such that 00 g of polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.5 to 50 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A]. A particularly preferable amount is 1 to 20 moles.

The electron donor [C] is used in an amount of 0.1 to 50 mol, preferably 0.5 to 50 mol, particularly preferably 1 to 50 mol, per mol of titanium atom in the solid titanium catalyst component [A]. Used as needed.

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. Alicyclic hydrocarbons include: 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.
1 Preferably about -20 to 80°C, more preferably 0 to 80°C
A range of 40°C is desirable.

In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 35°C is about 0.2 dl/g or more,
Preferably, it is used in an amount of about 0.5 to 1 Odl/g.

The prepolymerization is carried out using the solid titanium catalyst component "A" as described above.
About 0.1-500g per 11g, preferably about 0.3-500g
It is desirable to carry out the reaction in such a way that 300 g, particularly preferably 1 to 100 g, of polymer are produced. If the amount of prepolymerization is too large, the production efficiency of the olefin polymer may decrease.

Prepolymerization can be carried out batchwise or continuously.

Olefins that can be used in this polymerization include ethylene, propylene, 1-butene, 4-methyl-
Examples include olefins having 2 to 20 carbon atoms, such as 1-pentene, 1-octene, and 3-methyl-1-butene. 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 that is liquid at the reaction temperature can also be used.

In the polymerization method of the present invention, the solid titanium catalyst component [
A] is the polymerization volume II! Usually about 0.001 to 0.5 mmol, preferably about 0.000 mmol per titanium atom.
005-0, used in an amount of 1 mmol. In addition, the organometallic compound [B] usually contains about 1 to 20 metal atoms per mole of titanium atoms in the prepolymerization catalyst component in the polymerization system.
00 moles, preferably about 1 to 500 moles. Furthermore, the electron donor [C] is used if necessary, and in that case, it is usually about 0.001 to 10 mol per mol of metal atom in the organometallic compound [B].
Preferably about 0.01 to 2 mol, particularly preferably about 0
．． It is used in an amount of 0.5 to 1 mole.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted and a polymer with a high melt flow rate can be obtained.

In the present invention, the polymerization temperature of the olefin is usually about 2
The pressure is usually set at 0 to 200° C., preferably about 50 to 100° C., and the pressure is usually set at normal pressure to 100 kg/cffl, preferably about 2 to 50 kg/cnf. In the polymerization method of the present invention, polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be a homopolymer, a random copolymer, a block copolymer, or the like.

When olefin polymerization, particularly propylene polymerization, is carried out using the above-mentioned olefin polymerization catalyst, the isotactic index (I
A propylene polymer having I) of 0 to 100% is obtained. At this time, stereoregularity can be easily controlled by adjusting the amount of electron donor [C] as necessary.

In addition, in the present invention, since the yield of the polymer per olefin polymerization catalyst is high, there is little catalyst residue in the polymer, and therefore, even if the operation for removing the catalyst in the polymer is omitted, there is no coloring caused by the catalyst. A white olefin polymer is obtained.

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

Example 1 [Preparation of solid catalyst component (A)] Activated halogen-containing magnesium compound [I[] was prepared by vibrating 20 g of magnesium chloride in a vibration mill for 8 hours and pulverizing the magnesium chloride. Prepared.

Meanwhile, 5g of titanium trichloride was purified with 35rrL of n-hexane.
Add purified pyridine 10 while suspending it in
After stirring and mixing at room temperature for 16 hours, the resulting solid was filtered and washed five times with purified hexane to prepare a titanium trichloride/pyridine complex.

The purified n
-Hexane 40ml 17. 3 g of magnesium chloride subjected to the above pulverization treatment and a 1 mol/l hexane solution of ethylaluminum sesquichloride equivalent to 76.6 mmol were added, and while stirring and mixing at O''C, the titanium trichloride/pyridine complex was converted into titanium atoms. Add 0.766 mmol, 16
Stir for hours. After filtering the obtained solid substance, it was transferred to the reactor again, and 40 mj' of purified n-hexane was added.
Add a 1 mol/l hexane solution of ethylaluminum sesquichloride equivalent to 76.6 mmol at 0°C,
Stir for hours. The obtained solid material was thoroughly washed with n-hexane to obtain a solid catalyst component (A). The composition of the solid catalyst component (A) was 0.6% by weight of titanium, 18% by weight of magnesium, and 68% by weight of chlorine.

[Purified n-hexane 500ml in an autoclave with an internal volume of 21ml]
rnI was charged, and 0.4 mmol of triethylaluminum and 0.0005 mmol of the above solid catalyst component (A) in terms of titanium atoms were charged at 40°C in a propylene atmosphere, and propylene polymerization was carried out for 1 hour. . The pressure during polymerization was kept at 7 Kg/alG.

After the polymerization was completed, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The obtained polymer was collected by filtration, washing with methanol, and drying under reduced pressure.

The yield of the obtained polymer was 2.1 g, thus the activity was 530 g/g-cat, the extraction residue with boiling octane was 0%, and the intrinsic viscosity [η] measured in decalin at 135 °C was 1. It was .97.

Example 2 [Preparation of solid catalyst component (B)] 0.15 in terms of titanium atom of solid catalyst component (B)
7 mmol was transferred to a 200 ml glass reactor purged with nitrogen, 30 mm of n-hexane was added, and 15.7 mm of a 1 mol/l hexane solution of ethylaluminum sesquichloride was added at 0°C, followed by stirring for 16 hours. . The obtained solid material was thoroughly washed with n-hexane to obtain a solid catalyst component (B). The composition of the solid catalyst component (B) is 0.7% by weight of titanium, 21% by weight of magnesium,
The chlorine content was 68% by weight.

[Polymerization] Example 1 except that solid titanium catalyst component (B) was used.
Polymerization of propylene was carried out in the same manner.

The yield of the obtained polymer was 2.7 g, therefore the activity was 790 g/g-cut, the extraction residue with boiling octane was 0%, and the intrinsic viscosity [η] measured in decalin at 135 °C was 2.07. Met.

Comparative Example 1 [Preparation of solid catalyst component (C)] Activated halogen-containing magnesium compound [II] was prepared by vibrating 20 g of magnesium chloride in a vibration mill for 8 hours and pulverizing the magnesium chloride. did.

On the other hand, while suspending 5 g of titanium trichloride in 35 yd of purified n-hexane, 10 mt' of purified pyridine was added,
After stirring and mixing at room temperature for 16 hours, the resulting solid was filtered and washed five times with purified hexane to prepare a titanium trichloride/pyridine complex.

66.5 d of purified n-hexane, 5 g of magnesium chloride subjected to the above pulverization treatment, and 0.046 mmol of titanium trichloride/pyridine complex in terms of titanium atoms were added to a 200-mm glass reactor purged with nitrogen, and the mixture was heated at 0°C. While stirring and mixing, a 1 mol/l hexane solution of ethylaluminum sesquichloride equivalent to 10 mmol was added, and the mixture was stirred for 16 hours. The solid catalyst component (C) was obtained by thoroughly washing the obtained solid substance with n-hexane. The composition of the solid catalyst component (C) was 0.043% by weight of titanium, 24% by weight of magnesium, and 69% by weight of chlorine.

[Purified n-hexane 500ml in an autoclave with an internal volume of 21ml]
-, 0.4 mmol of triethylaluminum, the above solid catalyst component (
C) was charged at 0.0005 mmol in terms of titanium atoms,
Propylene polymerization was carried out for 1 hour. The pressure during polymerization is 7k
g/corG.

After the polymerization was completed, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The obtained polymer was collected by filtration, washing with methanol, and drying under reduced pressure.

The yield of the obtained polymer was 11.9 g1u, so the activity was 210 g/g-cat, the extraction residue with boiling octane was 0%, and the intrinsic viscosity [η] measured in decalin at 135°C was 1. It was 88.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (2)

[Claims] (1) [A] [I] Titanium trichloride and electron donor (a)
A titanium complex compound obtained by contacting [II] a halogen-containing magnesium compound, and [III] an organometallic compound, containing at least magnesium, a halogen, and trivalent titanium, and having a titanium content of 0.5% by weight. % of a solid titanium catalyst component, [B] an organometallic compound, and optionally [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.