JPH05279418A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To efficiently obtain a polyolefin, especially a linear low-density polyolefin without using a large amount of an organometallic compound by using a highly active catalyst consisting essentially of a Ti compound, a specific compound and an organoaluminum compound. CONSTITUTION:An olefin is polymerized preferably at 20-250 deg.C under 0-100kg/ cm<2>G by using a catalyst consisting essentially of (A) a Ti compound [preferably bis(cyclopentadienyl)dimethyltitanium], (B) a compound (preferably triethyl ammonium tetraphenylborate) and (C) an organoaluminum compound (preferably triisobutylaluiminum). The amounts of the components A and B to be used are 0.0001-1millimol/l, respectively, that of the component C is 0.05-100millimol/l expressed in terms of Al atom and the molar ratio of the component B/A is 0.5-10 and that of the component C/A is 5-100.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing a polyolefin. More specifically, the present invention relates to a method for efficiently producing a polyolefin, particularly a linear low density polyethylene, with a highly active catalyst without using a large amount of an organometallic compound.

[0002]

2. Description of the Related Art Recently, a catalyst composed of a metallocene compound of a transition metal and an aluminoxane has been proposed as a new homogeneous catalyst (Japanese Patent Laid-Open No. 58-19309). Although this catalyst has extremely high activity and excellent copolymerizability, it has a drawback that it requires a large amount of aluminoxane.

On the other hand, a method for polymerizing an α-olefin using a specific boron complex containing ammonium and a metallocene compound as a catalyst has been disclosed (Japanese Patent Publication No. 1-502).
No. 036). However, the catalyst used in this method has a problem that the polymerization activity is extremely low and it is difficult to industrially utilize.

[0004]

Under the above circumstances, the present invention efficiently uses a highly active catalyst to obtain a polyolefin, particularly a linear low density polyethylene, without using a large amount of an organometallic compound. It is made for the purpose of providing a manufacturing method.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and first, as a method for efficiently producing an olefin polymer without using a large amount of an organoaluminum compound. , A transition metal compound, a compound that reacts with a transition metal compound to form an ionic complex, and a catalyst containing an organoaluminum compound as a main component have been proposed (Japanese Patent Application No. 3-339523).

As a result of further studies, the present inventors have found that a titanium compound, a compound that reacts with a titanium compound to form an ionic complex, and a catalyst containing an organoaluminum compound as main components, or contact with these catalysts. It was found that the object can be achieved by using a catalyst composed of the obtained reaction product, and the present invention has been completed based on this finding.

That is, the present invention uses (A) a titanium compound, (B) a compound which reacts with a transition metal compound to form an ionic complex, and (C) an organoaluminum compound as a main component of an olefin. And a method for producing a polyolefin, characterized in that (A)
The present invention provides a method for producing a polyolefin, which comprises polymerizing an olefin by using a reaction product obtained by bringing the component, the component (B) and the component (C) into contact with each other as a catalyst.

The titanium compound used as the catalyst component (A) in the method of the present invention has a general formula of CpTiR ¹ aR ² bR ³ c (I) Cp ₂ TiR ¹ aR ² b (II) (Cp-Ae-Cp) TiR. A cyclopentadienyl compound represented by ¹ aR ² b (III) or a derivative thereof, or a compound represented by the general formula TiR ¹ aR ² bR ³ cR ⁴ d (IV) or a derivative thereof is preferable.

In the above general formulas (I) to (IV), C
p is a cyclic unsaturated hydrocarbon group such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group, or a chain An unsaturated hydrocarbon group is shown. R ¹ , R ² ,
R ³ and R ⁴ each represent a ligand such as a σ-bonding ligand, a chelating ligand, and a Lewis base. Specific examples of the σ-bonding ligand include a hydrogen atom and an oxygen atom. , Halogen atom, alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Alkoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, 1 to 1 carbon atoms
Examples thereof include 20 acyloxy groups, allyl groups, substituted allyl groups, and substituents containing a silicon atom, and examples of chelating ligands include acetylacetonato groups and substituted acetylacetonato groups. A indicates crosslinking by covalent bond. a, b, c and d are 0 or 1 to 4 respectively
An integer. e represents 0 or an integer of 1 to 6. R ¹ , R ² ,
Two or more of R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. (I
In the formulas I) and III, the two Cp's may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group and 1,2-dimethylcyclohexyl group. Pentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group,
1,2,3-trimethylcyclopentadienyl group, 1,
2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. In addition, the above (I)
Specific examples of R ^{1 to} R ^{4 in} the formulas (IV) to (IV) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as the halogen atom; a methyl group, an ethyl group, and n- as the alkyl group having 1 to 20 carbon atoms. Propyl group, isopropyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, alkylaryl group or Phenyl group, tolyl group, xylyl group, benzyl group as arylalkyl group; heptadecylcarbonyloxy group as acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as substituent containing silicon atom, (trimethylsilyl) methyl group; as Lewis base Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, acetonitrile,
Nitriles such as benzonitrile, trimethylamine,
Amines such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2'-bipyridine, phenanthroline, phosphines such as triethylphosphine and triphenylphosphine; ethylene, butadiene as chain unsaturated hydrocarbons, 1 -Penten,
Isoprene, pentadiene, 1-hexene and their derivatives; examples of cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and their derivatives. In addition, the above (I
Examples of the crosslink by A covalent bond in the formula II) include methylene bridge, dimethylmethylene bridge, ethylene bridge, 1,1′-cyclohexylene bridge, dimethylsilylene bridge, dimethylgermylene bridge and dimethylstannylene bridge. ..

Examples of the compound represented by the general formula (I) include (pentamethylcyclopentadienyl).
Trimethyltitanium, (pentamethylcyclopentadienyl) triphenyltitanium, (pentamethylcyclopentadienyl) tribenzyltitanium, (pentamethylcyclopentadienyl) trichlorotitanium,
(Pentamethylcyclopentadienyl) trimethoxytitanium, (cyclopentadienyl) trimethyltitanium, (cyclopentadienyl) triphenyltitanium, (cyclopentadienyl) tribenzyltitanium, (cyclopentadienyl) trichlorotitanium,
(Cyclopentadienyl) trimethoxytitanium,
(Cyclopentadienyl) dimethyl (methoxy) titanium, (methylcyclopentadienyl) trimethyltitanium, (methylcyclopentadienyl) triphenyltitanium, (methylcyclopentadienyl) tribenzyltitanium, (methylcyclopentadienyl) ) Trichlorotitanium, (methylcyclopentadienyl) dimethyl (methoxy) titanium, (dimethylcyclopentadienyl) trichlorotitanium, (trimethylcyclopentadienyl) trichlorotitanium, (trimethylsilylcyclopentadienyl) trimethyltitanium, (tetramethyl Cyclopentadienyl) trichlorotitanium and the like.

Examples of the compound represented by the general formula (II) include bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) diethyltitanium and bis (cyclo). Pentadienyl) dibenzyltitanium, Bis (cyclopentadienyl) dimethoxytitanium, Bis (cyclopentadienyl) dichlorotitanium, Bis (cyclopentadienyl) dihydridotitanium, Bis (cyclopentadienyl) monochloromonohydridotitanium , Bis (methylcyclopentadienyl) dimethyltitanium, bis (methylcyclopentadienyl) dichlorotitanium, bis (methylcyclopentadienyl) dibenzyltitanium, bis (pentamethylcyclopentadiene Nil) dimethyltitanium, bis (pentamethylcyclopentadienyl) dichlorotitanium, bis (pentamethylcyclopentadienyl) dibenzyltitanium, bis (pentamethylcyclopentadienyl) chloromethyltitanium, bis (pentamethylcyclopentadiene (Enyl) hydridomethyl titanium,
(Cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorotitanium and the like can be mentioned.

Examples of the compound represented by the general formula (III) include ethylenebis (indenyl) dimethyltitanium, ethylenebis (indenyl) dichlorotitanium, ethylenebis (tetrahydroindenyl) dimethyltitanium, ethylenebis (tetrahydroindene). Nil) dichlorotitanium, dimethylsilylenebis (cyclopentadienyl) dimethyltitanium, dimethylsilylenebis (cyclopentadienyl) dichlorotitanium, isopropylidene (cyclopentadienyl)
(9-Fluorenyl) dimethyltitanium, isopropylidene (cyclopentadienyl) (9-fluorenyl)
Dichlorotitanium, [phenyl (methyl) methylene]
(9-Fluorenyl) (cyclopentadienyl) dimethyltitanium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyltitanium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyltitanium, cyclohexalidene (9 -Fluorenyl) (cyclopentadienyl) dimethyltitanium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethyltitanium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethyltitanium, dimethylsilylene (9-fluorenyl)
(Cyclopentadienyl) dimethyltitanium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorotitanium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethyltitanium, dimethylsilylene Examples thereof include bis (indenyl) dichlorotitanium.

Further, examples of the compound represented by the general formula (IV) include tetramethyltitanium, tetrabenzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium,
Tetrachlorotitanium, tetrabromotitanium, butoxytrichlorotitanium, dibutoxydichlorotitanium, bis (2,5-di-t-butylphenoxy) dimethyltitanium, bis (2,5-di-t-butylphenoxy) dichlorotitanium, titanium Examples thereof include bis (acetylacetonate).

Further, in the present invention, as the catalyst component (A), two substituted or unsubstituted co- throwing cyclopentadienyl groups (provided that at least one is substituted cyclopenta) in the general formula (III) are used. A titanium compound having a multicoordinating compound, which is a pentadienyl group) bonded to each other through an element selected from Group IVA of the periodic table, as a ligand can be preferably used, and thereby isotacticity can be obtained. It is possible to obtain an isotactic polyolefin having a high city, a high molecular weight, and a high melting point.

Examples of such compounds include those represented by the general formula:

[Chemical 1] The compound represented by or its derivative can be mentioned.

Y in the general formula (V) is carbon, silicon,
Germanium or tin ^{_{atom, R 5 t -C 5 H 4}} -t and ^{_{R 5 u -C 5 H 4-}} u are each a substituted cyclopentadienyl group, t and u is an integer of 1-4. Where R ⁵
Represents a hydrogen atom, a silyl group or a hydrocarbon group, and may be the same or different. Further, in at least one of the cyclopentadienyl groups, R ⁵ is present on at least one carbon adjacent to the carbon bonded to Y.
R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group. X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, or an alkoxy group having 1 to 20 carbon atoms. X may be the same or different from each other, and R ⁶ may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (V) include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group. Group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group,
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X include P, Cl, Br, I as a halogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, octyl group as an alkyl group having 1 to 20 carbon atoms, 2 -Ethylhexyl group; a methoxy group as an alkoxy group having 1 to 20 carbon atoms,
An ethoxy group, a propoxy group, a butoxy group, a phenoxy group; a phenyl group, a tolyl group, a xylyl group, a benzyl group and the like as an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms. Specific examples of R ⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group and the like.

Examples of the compound represented by the general formula (V) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride.

In the method of the present invention, a compound which reacts with a transition metal compound to form an ionic complex is used as the catalyst component (B). As this compound, any compound can be used as long as it can react with the titanium compound of the catalyst component (A) to form an ionic complex, and a cation and an anion in which a plurality of groups are bound to an element are used. It is possible to preferably use a compound consisting of, particularly a coordination complex compound consisting of a cation and an anion in which a plurality of groups are bound to an element. As a compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the general formula ([L ¹ -R ⁷ ] ^{K +} ) p ([M ³ Z ¹ Z ² ... Z ⁿ ]
^{(N-m) -) q} (VI) ([L 2] K +) p ([M
^{4 Z 1 Z 2 ... Z n} ] (n-m) -) q (VII)
A compound represented by the formula (L ² in the formula is M ⁵ , R ⁸ R ⁹ M ⁶ , R ¹⁰ ₃ C or R ¹¹ M ⁶ ) can be preferably used.

In the above general formulas (VI) and (VII), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group, VIIB group, VIII group and IB of the periodic table, respectively.
An element selected from Group IIIB, Group IIIB, Group IIIA, Group IVA and Group VA, preferably Group IIIA, Group IVA and Group VA
The elements selected from the group, M ⁵ and M ^6, are IIIB group, IVB group, VB group, VIB group and VIIB group of the periodic table, respectively.
Group, VIII group, IA group, IB group, IB group, IIA group, IIB group and VIIA group, Z ^{1 to} Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number 6 To C20 aryloxy group, C1 to C20 alkyl group, C6 to C20 aryl group, alkylaryl group, arylalkyl group, C1 to C20 halogen substituted hydrocarbon group, C1 to C20 2 represents an acyloxy group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷ is a hydrogen atom, having 1 to 20 carbon atoms
Represents an alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ⁸ and R
⁹ is a cyclopentadienyl group, substituted cyclopentadienyl is an indenyl group or a fluorenyl group, R is
¹⁰ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹
Represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. m is the valence of M ³ and M ⁴ , and is 1 to 7.
, N is an integer of 2 to 8, k is [L ¹ -R ⁷ ], [L
² ] is an integer of 1 to 7 in ion valence, p is an integer of 1 or more,
q = (p × k) / (nm).

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Examples thereof include phosphines such as fin, triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethylthioether and tetrahydrothiophene, and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ include B, Al, Si,
P, As, Sb, etc., preferably B or P, M ⁵ are specific examples of Li, Na, Ag, Cu, Br, I, etc., M
Specific examples of ⁶ include Mn, Fe, Co, Ni and Zn.

Specific examples of Z ^{1 to} Z ⁿ include a dimethylamino group and a diethylamino group as the dialkylamino group;
A methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; a phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 6 to 20 carbon atoms; As an alkyl group of, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl group; as an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group Phenyl group,
p-tolyl group, benzyl group, 4-t-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; carbon number 1-20 halogen-substituted hydrocarbon groups such as p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-
Trifluorophenyl group, pentafluorophenyl group,
3,5-di (trifluoromethyl) phenyl group; F, Cl, Br, I as halogen atom; pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron as organic metalloid group Groups.
Specific examples of R ⁷ and R ¹⁰ include the same as those mentioned above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Be done. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups is 1 to 5.

Of the compounds represented by the general formulas (VI) and (VII), those in which M ³ and M ⁴ are boron are preferable. Preferred examples of the compound represented by the general formula (VI) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate and methyltriphenylborate. (N-Butyl) ammonium, benzyl triphenylborate tri (n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzyl tetraphenylborate Pyridinium, methyl tetraphenylborate (2-cyanopyridinium), trimethylsulfonium tetraphenylborate , Tetraphenylborate benzyl dimethyl sulfonium, tetra (pentafluorophenyl)
Triethylammonium borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (tetraethyl Ammonium), tetra (pentafluorophenyl) borate [methyltri (n-butyl)]
Ammonium], tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], methyldiphenylammonium tetra (pentafluorophenyl) borate, methyltriphenylammonium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate Dimethyldiphenylammonium, Anilinium tetra (pentafluorophenyl) borate, Methylanilinium tetra (pentafluorophenyl) borate, Dimethylanilinium tetra (pentafluorophenyl) borate, Trimethylanilinium tetra (pentafluorophenyl) borate, Tetra (pentafluoro Phenyl) dimethyl borate (m-nitroanilinium), dimethyl tetra (pentafluorophenyl) borate (p-bromoanilinium), Pyridinium tra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) borate (p-cyanopyridinium), Tetra (pentafluorophenyl) borate (N-methylpyridinium), Tetra (pentafluorophenyl) borate (N-benzylpyridinium) , Tetra (pentafluorophenyl) boric acid (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-methylpyridinium), tetra (pentafluorophenyl) borate (p-
Cyano-N-benzylpyridinium), trimethylsulfonium tetra (pentafluorophenyl) borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetraphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate , Tetra (3
Examples thereof include dimethylanilinium 5-ditrifluoromethylphenyl) borate and triethylammonium hexafluoroarsenate.

Preferred examples of the compound represented by the general formula (VII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese) and tetra (pentafluoro). Phenyl) ferrocenium borate, tetra (pentafluorophenyl) borate (1,1'-dimethylferrocenium), decamethylferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Acetylferrocenium borate, formylferrocenium tetra (pentafluorophenyl) borate, cyanoferrocenium tetra (pentafluorophenyl) borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, tetra ( Lithium pentafluorophenyl) borate, sodium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) ) Boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate and the like can be mentioned.

Further, the above general formulas (VI) and (VII)
Compounds other than, for example, tri (pentafluorophenyl)
Boron, tri [3,5-di (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used.

In the method of the present invention, the organoaluminum compound used as the component (C) is represented by the general formula R ¹² rAlQ _3-r (VIII) (wherein R ¹² has 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms).
Hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, and arylalkyl groups, Q is a hydrogen atom, and has 1 to 1 carbon atoms.
20 alkoxy groups or halogen atoms, where r is 1 to
A compound represented by the general formula

[0028]

[Chemical 2] (R ¹² in the formula has the same meaning as described above, s represents the degree of polymerization, and is usually 3 to 50, preferably 7 to 40)
A chain aluminoxane represented by, and a general formula

[Chemical 3] The cyclic alkylaminoxane represented by the formula (R ¹² and s in the formula have the same meanings as described above).

Specific examples of the compound represented by the general formula (III) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride and dimethyl. Examples thereof include aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride.

Among the compounds represented by the above general formulas (VIII), (IX) and (X), preferred are aluminum compounds containing an alkyl group having at least one alkyl group having 3 or more carbon atoms, especially at least one branched alkyl group. Alternatively, it is an aluminoxane. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When using this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof,
High activity can be obtained.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be carried out according to a known method. For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added at the time of polymerization and then water is added, and (3) a metal salt There is a method of reacting water of crystallization contained in, etc., water of adsorption to an inorganic substance or an organic substance with an organoaluminum compound, and (4) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water.

In the method of the present invention, as the polymerization catalyst,
(1) You may use the catalyst which consists of a combination of said (A) component, (B) component, and (C) component, (2) The said (A)
A reaction product obtained by previously contacting the component, the component (B) and the component (C) may be used.

Regarding the amount of each catalyst component used in the method (1), the component (A) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the component (B) is 0. 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and component (C) in the range of 0.01 to 500 mmol / liter, preferably 0.05 to 100 mmol / liter in terms of Al atom. And the (B) component / (A) component molar ratio is 0.01 to 100, preferably 0.5 to 10 and the (C) component / (A) component molar ratio is 0.1 to 2000, preferably 5 It is desirable to use each component so as to be in the range of up to 1000.

On the other hand, in the method (2), the components (A), (B) and (C) are brought into contact with each other in an inert solvent in an inert gas atmosphere.
The component (A) is 0.01 to 100 mmol / liter,
It is desirable to use each component so that the component (B) is in the range of 0.01 to 100 mmol / liter and the component (C) is in the range of 0.1 to 1000 mmol / liter in terms of Al atom. 0.5 <[B] / [Ti] <5 0.5 <[Al _R ] / [Ti] <500 and 0.1 mmol / liter <[Ti] [where [Ti] is () A) the molar concentration of the component,
[B] is the molar concentration of the component (B) in the contact field, [Al _R ]
Is the molar concentration of component (C) in the contact field (calculated as Al atoms)], the resulting contact product has markedly improved polymerization activity.

If [B] / [Ti] is 0.5 or less, the activity improving effect is not recognized, and if it is 5 or more, the component (B) is wasted. Further, [Al _R ] / [Ti] is 0.
If it is 5 or less, the activity improving effect is insufficient, and if it is 500 or more, the component (C) is wasted and a large amount of Al component remains in the product polymer. Furthermore, [Ti] is 0.1
If it is less than millimole / liter, the contact reaction rate is slow and it is difficult to sufficiently exert the activity improving effect.

Examples of the inert solvent used for bringing the respective components into contact include aliphatic hydrocarbons having 5 to 18 carbon atoms, alicyclic hydrocarbons, aromatic hydrocarbons, and the like.
Specific examples include n-pentane, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene, etc. These may be used alone or in combination of two or more. You may use.

The contact temperature and reaction time are not particularly limited, and the order of contacting each component is not particularly limited, and the components can be contacted in any order.
Further, the contact treatment may be carried out by so-called prepolymerization in the presence of a small amount of monomer or under the condition that the polymerization reaction is extremely slow. The contact-treated product thus prepared can be stored under an inert gas atmosphere.

In the method of the present invention, a polyolefin is produced by polymerizing an olefin in the presence of the polymerization catalyst prepared by the above method (1) or (2). There is no particular limitation on the kind of the olefin, for example, having 2 to 10 carbon atoms
.Alpha.-olefins and the like, and these olefins may contain, as comonomers, dienes such as butadiene, isoprene, chloroprene, and ethylidene norbornene, but the method of the present invention is preferably ethylene-based. It is preferably applied to the production of polymers, especially linear low density polyethylene.

In the production of the ethylene polymer, ethylene may be polymerized alone, or ethylene and other α may be polymerized.
-It may be copolymerized with an olefin or a diene compound.
Examples of the α-olefin include linear or branched monoolefins having 3 to 18 carbon atoms, and α-olefins substituted with an aromatic nucleus. Specific examples of such α-olefins include propylene, butene-1,
Hexene-1, octene-1, nonene-1, decene-
1, linear monoolefins such as 1, undecene-1, dodecene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, 2-ethylhexene-
Mention may be made of branched chain monoolefins such as 1,2,2,4-trimethylpentene-1 and further monoolefins substituted with aromatic nuclei such as styrene.

The diene compound is preferably a non-conjugated diolefin having a linear or branched chain having 6 to 20 carbon atoms. Specifically, 1,5-hexadiene,
1,6-heptadiene, 1,7-octadiene, 1,8
-Nonadiene, 1,9-decadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-dimethyl-4-t-
Butyl-2,6-heptadiene and further 1,5,9-
Polyenes such as decatriene and endomethylene-based cyclic dienes such as 5-vinyl-2-norbornene can be used.

The polymerization method is not particularly limited, and any polymerization method such as slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method and the like can be adopted. As the polymerization solvent, an inert solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon is used, and among these, an aliphatic hydrocarbon such as hexane or heptane is preferable.

When the contact product obtained by the above method (2) is used as the polymerization catalyst, it is converted into Ti atoms of 10
⁻⁸ to 10 ⁻³ mol / liter, preferably 10 ⁻⁷ to
It is preferable to use it in the range of 10 ⁻⁴ mol / liter.

The polymerization temperature is not particularly limited, but it is usually selected in the range of 0 to 350 ° C, preferably 20 to 250 ° C. On the other hand, the polymerization pressure is not particularly limited, but is usually 0 to 150 kg / cm ² G, preferably 0.
It is selected in the range of up to 100 kg / cm ² G.

The molecular weight can be adjusted by raising the polymerization temperature or by adding hydrogen, alkylaluminum, alkylzinc or the like during the polymerization, and it is particularly advantageous to add trialkylaluminum or alkylzinc. Is.

[0045]

According to the present invention, as a polymerization catalyst, a combination of a titanium compound, a compound which reacts with a transition metal compound to form an ionic complex, and an organoaluminum, particularly, the three components are contacted in advance. By using the reaction product obtained as described above, the catalytic activity is high without using a large amount of the organometallic compound, and the olefin can be efficiently polymerized, and particularly linear low density polyethylene can be industrially advantageously produced. it can.

[0046]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of dimethylanilinium tetra (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was added to 45 mmol of boron trichloride in hexane. To give tri (pentafluorophenyl) boron as a white solid.

Obtained tri (pentafluorophenyl)
41 mmol of boron and 4 of pentafluorophenyl lithium
Reaction with 1 mmol isolated lithium tetra (pentafluorophenyl) boron as a white solid.

Next, 16 mmol of lithium tetra (pentafluorophenyl) boron and dimethylaniline hydrochloride 1
By reacting with 6 mmol in water, 11.4 mmol of tetra (pentafluorophenyl) boron dimethylanilinium was obtained as a white solid. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the target product.

(2) Copolymerization of ethylene and 1-octene After the inside of a dry 1 liter polymerization reactor equipped with a stirrer was replaced with dry nitrogen, dry n-hexane (340 m) was used.
1 and 60 ml of 1-octene were charged and the temperature was raised to 60 ° C.

Triisobutylaluminum 1.0 mmo
1, 6.0 μmol of dimethylanilinium tetra (pentafluorophenyl) borate and 4.0 μmol of tetranormal butoxytitanium were added to the polymerization reactor and immediately heated to 80 ° C. Then, ethylene gas was introduced, and the total pressure was maintained at 8 kg / cm ² G and the temperature was 60 ° C. at 60 ° C.
Polymerization was carried out for a minute. Immediately after the completion of the polymerization, the pressure was released, and methanol was added to the polymerization reactor to stop the polymerization immediately. Replace the contents of the polymerization reactor with a large amount of ethanol.
The mixture was poured into a hydrochloric acid mixed solution for deashing. The polymer was filtered and separated, and dried under reduced pressure at 80 ° C. for 4 hours to obtain 0.43 g of an ethylene-1-octene copolymer. [Η] was 9.4.

Example 2 (1) Catalytic reaction of three components In 100 ml of Schlenk bin, 46.5 ml of hexane,
As the component (C), 1.0 ml of a hexane solution of triisobutylaluminum (1.0 mol / liter) was added.
Then, while stirring, 1.0 ml of a hexane solution of tetranormal butoxytitanium (0.1 mol / liter) was added as the component (A), and the mixture was stirred for 10 minutes. Further, as a component (B), a toluene solution of dimethylanilinium tetra (pentafluorophenyl) borate (1.0 mol /
Liter) 1.5 ml was added, and the mixture was stirred for 60 minutes to carry out a contact reaction. The obtained contact reaction product was aged in the dark at room temperature for 48 hours.

(2) Copolymerization of ethylene and 1-octene After replacing the inside of a dry 1 liter polymerization reactor with a stirrer with dry nitrogen, 340 ml of dry n-hexane
60 ml of 1-octene and 1.0 mmol of triisobutylaluminum were charged and the temperature was raised to 60 ° C.

2.0 ml (4 μm) of the catalytic reaction product of the above three components
mol-Ti) was added to the polymerization reactor and immediately
The temperature was raised to. Then, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 10 minutes while maintaining the total pressure at 8 kg / cm ² G. Immediately after the completion of the polymerization, the pressure was released, and methanol was added to the polymerization reactor to stop the polymerization immediately.
The contents of the polymerization reactor were put into a large amount of ethanol-hydrochloric acid mixed solution to be deashed. Polymer is filtered and separated, 80 ℃
After vacuum drying for 4 hours, 3.61 g of an ethylene-1-octene copolymer was obtained. [Η] was 11.8. ^Thirteen
Octene unit content 2.8 mol% determined from C-NMR
Met.

Comparative Example 1 The procedure of Example 2 was repeated except that dimethylanilinium tetra (pentafluorophenyl) borate was not used, and only a trace amount of the polymer was obtained.

Comparative Example 2 A polymer was not obtained by the same procedure as in Example 2 except that triisobutylaluminum was not used.

Comparative Example 3 The procedure of Example 2 was repeated except that tetranormal butoxyzirconium was used instead of tetranormal butoxytitanium, and only a trace amount of the polymer was obtained.

Example 3 The amount of the component (C) in the catalytic reaction field was changed. (1) Catalytic reaction of three components 3100 ml of hexane in 100 ml of Schlenk bin,
As the component (C), 10 ml of a hexane solution of triisobutylaluminum (1.0 mol / liter) was added. Then, while stirring, 1.0 ml of a hexane solution of tetranormal butoxytitanium (0.1 mol / liter) was added as the component (A), and the mixture was stirred for 10 minutes. Further, as a component (B), a toluene solution of dimethylanilinium tetra (pentafluorophenyl) borate (1.0 mol /
Liter) 1.5 ml was added, and the mixture was stirred for 60 minutes to carry out a contact reaction. The obtained contact reaction product was aged in the dark at room temperature for 24 hours.

(2) Copolymerization of ethylene and 1-octene Copolymerization was carried out in the same manner as in Example 2. 3.13 g of an ethylene-1-octene copolymer having [η] = 11.6 was obtained.

Example 4 The catalytic reaction of the three components was carried out in a toluene solvent. (1) Catalytic reaction of three components To 100 ml of Schlenk bin, 46.5 ml of toluene,
As the component (C), 1.0 ml of a hexane solution of triisobutylaluminum (1.0 mol / liter) was added.
Then, while stirring, 1.0 ml of a hexane solution of tetranormal butoxytitanium (0.1 mol / liter) was added as the component (A), and the mixture was stirred for 10 minutes. Further, as a component (B), a toluene solution of dimethylanilinium tetra (pentafluorophenyl) borate (1.0 mol /
Liter) 1.5 ml was added, and the mixture was stirred for 60 minutes to carry out a contact reaction. The obtained contact reaction product was immediately subjected to polymerization.

(2) Copolymerization of ethylene and 1-octene The amount of n-hexane was 370 ml, and the amount of 1-octene was 30 m.
Copolymerization was performed in the same manner as in Example 2 except that the amount was 1. 3.87 g of an ethylene-1-octene copolymer having [η] = 14.7 was obtained. ^The octene unit content determined from ¹³ C-NMR was 2.8 mol%.

Example 5 Triethylaluminum was used as the component (C). (1) Catalytic reaction of three components 4100 ml of hexane in 100 ml of Schlenk bin,
As the component (C), 1.0 ml of a hexane solution of triethylaluminum (1.0 mol / liter) was added. Then, while stirring, a hexane solution of tetranormal butoxytitanium as the component (A) (0.1 mol / liter)
1.0 ml was added and stirred for 10 minutes. Furthermore (B)
As a component, 1.5 ml of a toluene solution of dimethylanilinium tetra (pentafluorophenyl) borate (1.0 mol / liter) was added, and the mixture was further stirred for 60 minutes to carry out a contact reaction. The obtained contact reaction product was immediately subjected to polymerization.

(2) Copolymerization of ethylene and 1-octene Copolymerization was carried out in the same manner as in Example 2. 1.85 g of an ethylene-1-octene copolymer having [η] = 8.8 was obtained.

Example 6 Titanium tetrachloride was used as the component (A). (1) Catalytic reaction of three components To 100 ml of Schlenk bin, toluene 46.5 m
1, and 1.0 ml of a hexane solution of triisobutylaluminum (1.0 mol / liter) as the component (C) was added. Then, while stirring, 1.0 of a hexane solution of titanium tetrachloride (0.1 mol / liter) as the component (A) is added.
ml was added and stirred for 10 minutes. Further, component (B)
Toluene solution of dimethylanilinium tetra (pentafluorophenyl) borate (1.0 mol / liter) 1.5
After adding ml, the mixture was stirred for 60 minutes to carry out a contact reaction. The obtained contact reaction product was immediately subjected to polymerization.

(2) Copolymerization of ethylene and 1-octene Copolymerization was carried out in the same manner as in Example 2. 0.57 g of an ethylene-1-octene copolymer having [η] = 23.0 was obtained.

Example 7 Bis (cyclopentadienyl) dichlorotitanium was used as the component (A). (1) Copolymerization of ethylene and 1-octene After the inside of a dry 1 liter polymerization reactor equipped with a stirrer was replaced with dry nitrogen, 370 ml of dry toluene and 1
-Octene (30 ml) was charged and the temperature was raised to 60 ° C.

Triisobutylaluminum 1.0 mmo
1, 6.0 μmol of dimethylanilinium tetra (pentafluorophenyl) borate and 4.0 μmol of bis (cyclopentadienyl) dichlorotitanium were added to the polymerization reactor, and the temperature was immediately raised at 80 ° C. Then, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 15 minutes while maintaining the total pressure at 8 kg / cm ² G. Thereafter, the same procedure as in Example 1 was performed. 20.6 g of an ethylene-1-octene copolymer having [η] = 1.4 was obtained. ^The octene content determined from ¹³ C-NMR was 1.1 mol%.

Claims (4)

[Claims] 1. An olefin is polymerized by using a catalyst containing (A) a titanium compound, (B) a compound that reacts with a transition metal compound to form an ionic complex, and (C) an organoaluminum compound as main components. A method for producing a polyolefin, comprising: 2. The component (A) has a general formula of TiR ¹ aR ² bR ³ cR ⁴ d (wherein R ¹ a, R ² b, R ³ c and R ⁴ d are σ-bonding ligands, respectively). , Chelating ligands or Lewis bases, which may be the same or different from each other, and a, b, c and d are 0 or 1 to 4 respectively. The method for producing a polyolefin according to claim 1, which is a titanium compound represented by (an integer). 3. An olefin using as a catalyst a reaction product obtained by contacting (A) a titanium compound, (B) a compound that reacts with a transition metal compound to form an ionic complex, and (C) an organoaluminum compound. A method for producing a polyolefin, which comprises polymerizing. 4. The component (A) is represented by the general formula: TiR ¹ aR ² bR ³ cR ⁴ d (wherein R ¹ a, R ² b, R ³ c and R ⁴ d are σ-bonding ligands, respectively). , Chelating ligands or Lewis bases, which may be the same or different from each other, and a, b, c and d are 0 or 1 to 4 respectively. The method for producing a polyolefin according to claim 3, which is a titanium compound represented by (an integer).