JP3262137B2 - Method for producing ethylene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an ethylene polymer, and more particularly to a method for producing an ethylene polymer stably and efficiently without using a large amount of organoaluminum.

[0002]

2. Description of the Related Art In recent years, a catalyst comprising a metallocene compound of a transition metal and an aluminoxane has been proposed as a new homogeneous catalyst (JP-A-58-19309). This catalyst has very high activity and excellent copolymerizability, but has problems such as requiring a large amount of aluminoxane. On the other hand, a method of polymerizing an α-olefin using a specific boron complex containing ammonium and a metallocene compound as a catalyst is also disclosed (Japanese Patent Application Laid-Open No. 1-502036). However, the catalyst used in this method has a remarkably low polymerization activity, and is difficult to use industrially. Therefore, the research group of the present inventors has proposed a method for efficiently producing an α-olefin-based polymer without using a large amount of an organoaluminum compound. It has been proposed to use a compound which forms a complex of an organic compound and a catalyst mainly composed of an organic aluminum compound (Japanese Patent Application No. 3-339523). However, in this proposal, slurry polymerization is performed, and the resulting ethylene-based polymer may have poor operability such as adhering to a reaction vessel, and cannot be said to be a sufficiently efficient method for producing an ethylene-based polymer. . On the other hand, the operability has been improved,
As a method for efficiently producing a polymer, it has been proposed to use a catalyst in which a catalyst component is supported on a carrier (WO 91/09882, JP-A-3-234709).
Gazette, Japanese Patent Application No. 4-19558). However, in this method, special catalyst preparation equipment is required in order to support the catalyst component on the carrier, and a large equipment cost is required. Furthermore, since the preparation of the catalyst becomes complicated, a required catalyst cannot be sufficiently obtained.

[0003]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to solve the above problems, the periodic table IV
By using a catalyst containing a Group B transition metal compound, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound, by setting the polymerization temperature to a temperature equal to or higher than the melting point of the polymer to be formed. It was found that the desired ethylene polymer could be obtained. The present invention has been completed based on such findings.

That is, the present invention relates to a method for producing ethylene or a copolymer of ethylene with at least one α-olefin and / or a non-conjugated diene as a raw material, comprising the steps of: A metal compound, (b) a compound which reacts with a transition metal compound to form an ionic complex, and (c) an organoaluminum compound are used as main components and polymerized or copolymerized at a temperature not lower than the melting point of the ethylene polymer to be produced. An object of the present invention is to provide a method for producing an ethylene polymer, which is characterized by performing polymerization.

In the present invention, ethylene or ethylene and at least one α-olefin and / or
Alternatively, a non-conjugated diene is used. That is, ethylene may be used alone, ethylene may be used in combination with one or more other α-olefins, or ethylene may be used in combination with one or more non-conjugated dienes. Furthermore, ethylene, at least one α-olefin and at least one non-conjugated diene can be used. Where α
Examples of the olefin include propylene, 1-butene; 1-hexene; 1-octene; 1-nonene; 1-decene; 1-undecene; -Methylpentene-1; 4-methylpentene-1; 2-ethylhexene-
1; branched chain monoolefins such as 2,2,4-trimethylpentene-1 and the like, and monoolefins substituted with an aromatic nucleus such as styrene. In addition, as the non-conjugated diene, a non-conjugated diolefin having a straight or branched chain having 6 to 20 carbon atoms is preferable. For example, 1,5
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 the like. Further, a polyene such as 1,5,9-decatriene or an endmethylene cyclic diene such as 5-vinyl-2-norbornene can be used.

As the catalyst used in the present invention, (a)
Group IVB transition metal compounds of the Periodic Table, (b) Transition metal compounds
A compound which reacts with to form an ionic complex; and
(C) an organoaluminum compound is used as a main component
You. In the present invention, (a) a compound used as a catalyst component
The compound has the general formula CpMR¹ _aR^Two _bR^Three _c ... (I) Cp_TwoMR¹ _aR^Two _b ... (II) (Cp-A_e-Cp) MR¹ _aR^Two _b ... (III) or general formula MR¹ _aR^Two _bR^Three _cR^Four _d (IV) or a derivative thereof is preferable. The general
In the formulas (I) to (IV), M is titanium, zirconium
Or a transition metal from Group IVB of the periodic table such as hafnium.
And Cp is a cyclopentadienyl group, a substituted cyclopentane
Dienyl group, indenyl group, substituted indenyl group, tetra
Hydroindenyl group, substituted tetrahydroindenyl group,
Cyclic radicals such as fluorenyl or substituted fluorenyl
It represents a saturated hydrocarbon group or a chain unsaturated hydrocarbon group. R
¹, R^Two, R^ThreeAnd R^FourAre independent of each other
Ligands such as ligands, chelating ligands and Lewis bases
And the σ-binding ligand is specifically a hydrogen atom
, Oxygen atom, halogen atom, alkyl having 1 to 20 carbon atoms
Group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl, alkylaryl or aryl groups
Alkyl group, acyloxy group having 1 to 20 carbon atoms, allyl
Group, substituted allyl group, substituent containing silicon atom, etc.
Acetylacetate as a chelating ligand
For example, Tonert group and substituted acetylacetonate group
Wear. A represents a covalent crosslink. a, b, c and
And d are each independently 0 or an integer of 1 to 4. e is 0
Or an integer of 1 to 6. R¹, R^Two, R^ThreeAnd R^Four
And two or more of them may combine with each other to form a ring. Up
When Cp has a substituent, the substituent has 1 carbon atom.
~ 20 alkyl groups are preferred. Formulas (II) and (III)
In the formula, the two Cp may be the same,
They may be different from each other.

The substituted cyclopentadienyl groups in the above general formulas (I) to (III) include, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethyl Cyclopentadienyl group; tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group;
1,2,3-trimethylcyclopentadienyl group;
2,4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. 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 a halogen atom, and a methyl group, an ethyl group, and an n-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, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, a benzyl group as an arylalkyl group, a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms, a trimethylsilyl group, a (trimethylsilyl) methyl group as a substituent containing a silicon atom, and a Lewis base Dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, and acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethylaniline; pyridine; 2,2'-bipyridine; amines such as phenanthroline; triethylphosphine; phosphines such as triphenylphosphine; 1-pentene; isoprene; pentadiene; 1-hexene and their derivatives, benzene as cyclic unsaturated hydrocarbon;
Toluene; xylene; cycloheptatriene; cyclooctadiene; cyclooctatriene; cyclooctatetraene and derivatives thereof. Also,
Examples of the crosslink by a covalent bond of A in the above formula (III) include methylene bridge, dimethylmethylene bridge, ethylene bridge, 1,1′-cyclohexylene bridge, dimethylsilylene bridge, dimethylgermylene bridge, dimethylstannylene bridge and the like. Is mentioned.

That is, in the present invention, in producing ethylene or a copolymer of ethylene with at least one α-olefin and / or a non-conjugated diene, the present invention relates to (a) a catalyst represented by the general formula (I) to (IV) ) Expression
A group IVB transition metal compound represented by
(B) using the transition metal compound reacts with the general formula to form an ionic complex (VI) or (VII) a compound of the formula and (c) an organoaluminum compound as a main component, ethylene to be produced An object of the present invention is to provide a method for producing an ethylene polymer, which comprises polymerizing or copolymerizing at a temperature not lower than the melting point of the polymer. _{^{CpMR 1 a R 2 b R 3}} c ··· (I) Cp 2 MR 1 a R 2 b ··· (II) (Cp-A e -Cp) MR 1 a R 1 b ··· (III) MR ¹ _a R ² _b R ³ _c R ⁴ _d (IV) (where M is zirconium, titanium or hafnium
At least one IVB transition gold selected from the periodic table
Genus, Cp is a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group.
R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen group
Independently represents a σ-binding ligand or Lewis base;
They can be the same or different
No. A represents a covalent cross-link, and e represents an integer of 0 to 6.
Indicates a number. ) ([L ¹ -R ^{7] k} +) _p ^{([M 3 Z 1 Z 2 ·· Z} n ] ^(nm) _-) q · · · (VI) ([L ^{2] k} +) _p ([M ⁴ Z ¹ Z ² ·· Z ^{n] _{(nm) -) q ··· (}} VII) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 3 C or R
¹¹ M ⁶ ) wherein L ¹ is a Lewis base, M ³ and
Group VB respectively M ⁴ is the periodic table, VIB group, VIIB group, VIII
Group, IB, IIB, IIIA, IVA and VA
Elements, preferably from groups IIIA, IVA and VA
The selected elements, M ⁵ and M ^6, are each II in the periodic table.
IB, IVB, VB, VIB, VIIB, VIII, IA
Selected from group III, group IB, group IIA, group IIB and group VIIA
Element, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkyl amino
Group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl group having 1 to 20 carbon atoms, charcoal
Aryl group, alkylaryl group, ant having a prime number of 6 to 20
Ruarukiru group, a halogen location 換炭Kamizu C20
Element group, acyloxy group having 1 to 20 carbon atoms, organic metalloy
It indicates de group or a halogen atom, Z ¹ to Z ⁿ are the 2 following
The upper portions may be bonded to each other to form a ring. R ⁷ is water
Elemental atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl, alkylaryl or arylal
And R ⁸ and R ⁹ are each a cyclopentane
Dienyl group, substituted cyclopentadienyl group, indenyl
R ¹⁰ is an alkenyl group having 1 to 20 carbon atoms.
Kill group, aryl group, alkylaryl group or aryl
Represents an alkyl group. R ¹¹ is tetraphenylporphyri
And macrocyclic ligands such as phthalocyanine. m is M
^3, M ⁴ valences at 1-7 integer, n represents 2-8 integer,
k is the ionic valence of [L ¹ -R ⁷ ] and [L ² ] and is 1 to 7
Integer, p is an integer of 1 or more, q = (p × k) / (nm)
It is. )

Examples of the compound represented by the general formula (II) include bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) diphenyltitanium,
Bis (cyclopentadienyl) diethyl titanium, bis (cyclopentadienyl) dibenzyl titanium, bis (cyclopentadienyl) dimethoxy titanium, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) dihydride Titanium, bis (cyclopentadienyl) monochloromonohydridotitanium, bis (methylcyclopentadienyl) dimethyltitanium, bis (methylcyclopentadienyl) dichlorotitanium, bis (methylcyclopentadienyl) dibenzyltitanium, bis ( Pentamethylcyclopentadienyl) dimethyltitanium, bis (pentamethylcyclopentadienyl) dichlorotitanium, bis (pentamethylcyclopentadienyl) dibenzyltitanium, bis (pentamethylcyclopentadienyl) chloromethyltitanium, Scan (pentamethylcyclopentadienyl) hydridomethylsiloxanes titanium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorotitanium like, furthermore in these include compounds obtained by substituting titanium, zirconium or hafnium.

The compounds represented by the general formula (III) include, for example, ethylenebis (indenyl) dimethyltitanium, ethylenebis (indenyl) dichlorotitanium,
Ethylene bis (tetrahydroindenyl) dimethyltitanium, ethylenebis (tetrahydroindenyl) dichlorotitanium, dimethylsilylenebis (cyclopentadienyl) dimethyltitanium, dimethylsilylenebis (cyclopentadienyl) dichlorotitanium, isopropylidene (cyclopentadiene) Enyl) (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, dimethylsilylenebis (indenyl) dichlorotitanium and the like, and further, in these, compounds obtained by substituting titanium with zirconium or hafnium.

Further, as the compound represented by the general formula (IV), for example, tetramethyltitanium, tetrabenzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetrachlorotitanium, tetrabromotitanium, butoxytrichlorotitanium Titanium, butoxydichlorotitanium, bis (2,5-di-t-butylphenoxy) dimethyltitanium, bis (2,5-di-t-butylphenoxy) dichlorotitanium, titanium bis (acetylacetonate), and the like; , A compound in which titanium is replaced with zirconium or hafnium.

Further, in the present invention, as the catalyst component (a), in the general formula (III), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is substituted cyclopentadienyl group) A transition metal compound of Group IVB of the Periodic Table having a ligand as a multiple coordination compound bonded to each other via an element selected from Group IVA of the Periodic Table. . As such a compound, for example, a compound represented by the general formula (V)

[0013]

Embedded image

Or a derivative thereof.

In the general formula (V), Y is carbon, silicon,
Germanium or tin atom, R^Five _t-C_FiveH_4-tAnd
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadie.
The nyl group, t and u each represent an integer of 1-4. Where R
^FiveRepresents a hydrogen atom, a silyl group or a hydrocarbon group.
May be the same or different. Also, at least
And one of the cyclopentadienyl groups has a bond to Y
On at least one carbon next to the carbon^FiveExists
You. R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or
Represents an aryl group or an alkylaryl group having 6 to 20 carbon atoms.
Or an arylalkyl group. X is a hydrogen atom, halo
Gen atom, alkyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
0 aryl group, alkylaryl group or aryl
Represents an alkyl group or an alkoxyl group having 1 to 20 carbon atoms.
You. Xs may be the same or different from each other;
⁶May be the same or different from each other.

The substituted cyclopentadienyl group in the above general formula (V) includes, for example, methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
1,2,4-trimethylcyclopentadienyl group and the like. Specific examples of X include F, Cl, Br, I as a halogen atom, and methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, and 2 as alkyl groups having 1 to 20 carbon atoms. An ethylhexyl group, a methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group and arylalkyl group include phenyl group, tolyl group, xylyl group, and benzyl group. Specific examples of R ⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of such a compound of the general formula (V) include, for example, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, and a compound in which titanium is substituted with zirconium or hafnium.

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 form an ionic complex by reacting with the transition metal compound of Group IVB of the periodic table of the catalyst component (a). A compound comprising an anion bonded to an element, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bonded to the element can be suitably used. Examples of the compound such cations and a plurality of groups consisting of bound anions to elemental general formula ([L ¹ -R ^{7] k +)} _p ^{([M 3 Z 1 Z 2 ·· Z} n ] ^{(nm) -)} _q ··· (VI) or ([L ^{2] k} +) _p ^{([M 4 Z 1 Z 2 ·· Z} n ] _{^{(nm) -) q ··· (}} VII) ( where, L ² is M ^{5, R 8 R 9 M 6} , R 10 3 C or R
¹¹ M ⁶ is a) (wherein, L ¹ is a Lewis base, VB group of M ³ and M ⁴ respectively Periodic Table, VIB group, VIIB group, VIII
Group, IB group, IIB group, IIIA group, an element selected from Group IVA and VA group, preferably Group IIIA, elements selected from the Group IVA and VA group, M ⁵ and M ⁶ are II respectively Periodic Table
IB, IVB, VB, VIB, VIIB, VIII, IA
Group, IB, Group IIA, IIB and Group element selected from group VIIA, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms group, an organometalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
R ⁸ and R ⁹ are a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms. Group, aryl group, alkylaryl group or arylalkyl group. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. m is M
^3, M ⁴ valences at 1-7 integer, n represents 2-8 integer,
k is an ionic valence of [L ¹ -R ⁷ ] and [L ² ], and is an integer of 1 to 7, p is an integer of 1 or more, and q = (p × k) / (nm)
It is. ).

[0018] Here, specific examples of the Lewis base represented by L ^1, ammonia, methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, tri -n- butylamine, N , N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
Amines such as dimethylaniline; phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; ethylbenzoate And the like.

Further, specific examples of M ³ and M ⁴ include:
B, Al, Si, P, As, etc. Sb, preferably B or P, specific examples of M ⁵ are, Li, Na, Ag, C
Specific examples of M ⁶ such as u, Br, I include Mn, F
e, Co, Ni, Zn and the like. Specific examples of Z ¹ to Z ⁿ may, for example, as a dialkylamino group include a dimethylamino group, a diethylamino group, a methoxy group as an alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group, having 6 to 20 carbon atoms A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group, a methyl group as an alkyl group having 1 to 20 carbon atoms,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms, phenyl group as alkylaryl group or arylalkyl 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, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluoro as halogen-substituted hydrocarbon group having 1 to 20 carbon atoms Phenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, F, C
l, Br, I, pentamethylantimony group, trimethylsilyl group, trimethylgermyl group as organic metalloid groups,
Examples include a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ are the same as those described 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. Can be
Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups is an integer of 1 to 5.

Among the compounds of the above general formulas (VI) and (VII), those wherein M ³ and M ⁴ are boron are preferred. Among the compounds of the general formulas (VI) and (VII), the following compounds can be particularly preferably used. For example, compounds of the general formula (VI) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyltri (n-butyl) tetraphenylborate. Ammonium, benzyltriphenylborate tri (n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, Dimethylsulfonium, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate , Tetra (pentafluorophenyl)
Tetraethylammonium borate, tetra (pentafluorophenyl) borate [methyltri (n-butyl) ammonium] borate, tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], methyldiphenylammonium tetra (pentafluorophenyl) borate, Methyltriphenylammonium (pentafluorophenyl) borate, dimethyldiphenylammonium tetra (pentafluorophenyl) borate, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate Anilinium, trimethylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate (m-d Roanilinium), dimethyl tetra (pentafluorophenylmethyl) borate (p-bromoanilinium), pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetrafelphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-
And dimethylanilinium ditrifluoromethylphenyl) borate and triethylammonium tow hexafluoroarsenate.

On the other hand, the compounds of the general formula (VII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (manganese tetraphenylporphyrin), ferrocenium tetra (pentafluorophenyl) borate, Decamethylferrocenium (pentafluorophenyl) borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, cyanoferrocenium tetra (pentafluorophenyl) borate, tetra ( Silver pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Sodium borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate and the like. Compounds other than the general formulas (VI) and (VII) include, for example,
Tri (pentafluorophenyl) boric acid, tri [3,5-
[Di (trifluoromethyl) phenyl] boric acid, triphenyl boric acid and the like can also be used.

In the present invention, the organoaluminum compound used as the component (c) is represented by the general formula (VI)
II) R ¹² _r AlQ _3-r (VIII) (wherein R ¹² has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms)
A hydrocarbon group such as an alkyl group, an alkenyl group or an arylalkyl group, Q represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r represents a number of 1 to 3. ), A compound represented by the general formula (IX)

[0023]

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(Wherein, R ¹² is the same as described above. S represents the degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40). Formula (X)

[0025]

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(Wherein R ¹² and s are the same as described above).

Among the compounds represented by the general formulas (VIII), (IX) and (X), preferred are an alkyl group-containing aluminum compound having at least one alkyl group having 3 or more carbon atoms, especially a branched alkyl group. Aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof, high activity can be obtained. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be performed according to a known method. For example, a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organoaluminum compound at the beginning during polymerization and adding water later, water of crystallization contained in a metal salt or the like, There are a method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

Specific examples of the compound represented by the general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, and ethylaluminum. Dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride,
Ethyl aluminum sesquichloride and the like.

In the method of the present invention, as the (co) polymerization catalyst, a catalyst comprising a combination of (1) component (a), component (b) and component (c) may be used,
(2) A reaction product obtained by previously contacting the component (a), the component (b), and the component (c) may be used. Regarding the amount of each catalyst component used in the above method (1),
The component (a) is 0.0001 to 5 mmol / L, preferably 0.001 to 1 mmol / L, and the component (b) is
0.0001-5 mmol / l, preferably 0.000
1 to 1 mmol / liter and the component (c) is 0.01 to 500 mmol / liter in terms of Al atom, preferably
The molar ratio of component (b) / component (a) is 0.01 to 100, preferably 0.5 to 10 and preferably 0.5 to 10 and component (c) / component (a) mole. It is desirable to use each component such that the ratio is in the range of 0.1 to 2000, preferably 5 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 under an inert gas atmosphere.
(A) component is 0.01 to 100 mmol / l,
The component (b) is 0.01 to 100 mmol / l and the component (c) is 0.1 to 1000 mmol / l in terms of Al atom.
It is desirable to use each component so that it is in the range of liters, in particular the following conditions: 0.5 <[B] / [A] <5 0.5 <[C] / [A] <500 and 0.1 Mmol / liter <[A] (where [A] is the molar concentration of component (a) in the contact field, [B] is the molar concentration of component (b) in the contact field, [C]
Indicates the molar concentration of the component (c) in the contact field (in terms of Al atoms). When the condition (1) is satisfied, the obtained contact product has remarkably improved (co) polymerization activity. When the ratio [B] / [A] is 0.5 or less, no effect of improving activity is observed. When the ratio is 5 or more, (b)
Ingredients are wasted. [C] / [A] is 0.5
In the following, the effect of improving the activity is insufficient, and when it is 500 or more, the component (c) is wasted and a large amount of the Al component remains in the product polymer. Further, when [A] is less than 0.1 mmol / liter, the contact reaction rate is low, and it is difficult to sufficiently exert the activity improving effect.

The present invention is a method for producing an ethylene polymer using the above-mentioned raw materials and catalyst. In the (co) polymerization of the ethylene polymer, the above-mentioned raw materials and catalyst may be added to the reaction system, and polymerization or copolymerization may be performed at a temperature equal to or higher than the melting point of the ethylene polymer to be produced. This (co)
The polymerization temperature is not particularly limited as long as it is a temperature equal to or higher than the melting point of the ethylene polymer to be produced (the desired ethylene polymer), and is appropriately selected within this range. ° C, preferably 120-25
0 ° C. Here, if the temperature is lower than the melting point of the ethylene polymer, the produced polymer adheres to the inner wall of the reactor or the like, so that it is difficult to stably and efficiently produce the polymer. On the other hand, if the temperature is too high, such as over 350 ° C., the catalytic activity may decrease. Examples of the (co) polymerization method include various methods such as suspension polymerization, solution polymerization, and gas-phase polymerization. Among them, high-temperature solution polymerization is preferable. The method for adding the catalyst is not particularly limited, but it is preferable to dissolve the catalyst used for (co) polymerization in a solvent in advance. In the case of performing solution (co) polymerization, the polymerization solvent used may be any solvent used for normal polymerization of ethylene polymers, for example, aliphatic hydrocarbons such as hexane and heptane, and alicyclic hydrocarbons such as cyclohexane. Examples include inert solvents such as hydrogen, benzene, and aromatic hydrocarbons such as toluene. Also, a raw material monomer such as ethylene or α-olefin can be used as the solvent. Further, the pressure during (co) polymerization is not limited, but is usually 0 to 15
0 kg / cm ² G, preferably 0-100 kg / cm ²
G.

[0032]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples. Example 1 (1) Synthesis of dimethylanilinium tetra (pentafluorophenyl) borate Reaction of pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium with 45 mmol of boron trichloride in hexane. , Tri (pentafluorophenyl) boron as a white solid. Lithium tetra (pentafluorophenyl) boron was isolated as a white solid by reacting 41 mmol of the obtained tri (pentafluorophenyl) boron with 41 mmol of pentafluorophenyllithium. Next, 16 mmol of lithium tetra (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride were reacted in water to obtain 11.4 mmol of dimethylanilinium tetra (pentafluorophenyl) boron as a white solid. The fact that the product is the target product is determined by proton nuclear magnetic resonance measurement ( ¹ H-NM
R), and was confirmed by isotope carbon nuclear magnetic resonance measurement ( ^13C -NMR).

(2) Copolymerization of ethylene and 1-octene After replacing the inside of a dry 1 liter polymerization reactor equipped with a stirrer with dry argon, 420 ml of dry toluene and 60 ml of 1-octene were charged, and 15
The temperature was raised to 0 ° C. Dry toluene 2
0 ml, 0.5 ml of a hexane solution of triisobutylaluminum (1.0 mol / l), and a toluene dispersion (2.0 ml) of dimethylanilinium tetra (pentafluorophenyl) boron obtained in Example (1).
3.0 mmol, and 8 ml of a toluene solution of dicyclopentadienyl zirconium dichloride (0.5 mmol / l) were introduced into the polymerization reactor simultaneously with ethylene gas. Polymerization was carried out at 150 ° C. for 5 minutes while supplying ethylene gas so that the ethylene partial pressure was maintained at 24 kg / cm ² . After the completion of the polymerization, the polymerization was stopped by introducing an excessive amount of isopropanol. The contents of the polymerization reactor were poured into a large amount of methanol to demineralize. Filtration and separation of polymer, 80
Drying under reduced pressure at 4 ° C. for 4 hours gave 68.3 g of an ethylene-octene copolymer having a melting point of 124 ° C. 13 of the obtained polymer
The limiting viscosity number [η] in the solvent decalin at 5 ° C. is 0.66.
(Deciliter / g).

COMPARATIVE EXAMPLE 1 (1) Copolymerization of ethylene and 1-octene A dry 1 L polymerization reactor equipped with a stirrer was purged with dry nitrogen, and then 440 mL of dry toluene and 60 mL of 1-octene were added. 0.5 ml of a hexane solution of isobutylaluminum (1.0 mol / l) was charged, and the temperature was raised to 70 ° C. Next, the toluene dispersion of the dimethylanilinium tetra (pentafluorophenyl) borate obtained in Example 1 (1) (2.0
(Mmol / l) 1.5 ml and 4 ml of a toluene solution of dicyclopentadienyl zirconium dichloride (0.5 mmol / l) were immediately added, and the temperature was immediately raised to 80 ° C. Next, ethylene gas was introduced, and polymerization was carried out while maintaining the total pressure at 3 kg / cm ² G. After 15 minutes from the start of the polymerization, the temperature in the polymerization reactor could not be controlled to be constant. At this point, the polymerization was stopped. When the polymerization reactor was opened,
A large amount of the copolymer was found to adhere to the inner wall of the reactor and the stirring blade. The obtained copolymer was 32.5 g,
[Η] was 2.3 (deciliter / g).

Example 2 Polymerization was carried out in the same manner as in Example 1 except that dicyclopentadienyl zirconium dimethoxide was used instead of dicyclopentadienyl zirconium dichloride. 38.4 g of an ethylene-octene copolymer having a melting point of 124 ° C. was obtained. [Η] of the obtained polymer was 0.68 (deciliter / g).

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that triisobutylaluminum was not used. As a result, no polymer was obtained.

Example 3 (1) Catalytic reaction of three components In 100 ml of Schlenk bottle, hexane 46.
5 ml, (c) hexane solution of triisobutylaluminum as a catalyst component (1.0 mol / l) 1.
0 ml was added. Then, with stirring
(A) As a catalyst component, 1.0 ml of a hexane solution of tetranormal butoxytitanium (0.1 mol / l) was added, and the mixture was stirred for 10 minutes. Further, (b) 1.5 ml of a toluene dispersion (1.0 mol / l) of dimethylanilinium tetra (pentafluorophenyl) borate obtained in Example 1 (1) was added as a catalyst component. The contact reaction was performed by stirring for minutes. The resulting contact reaction product was aged for 15 hours at room temperature in the dark.

(2) Copolymerization of ethylene and 1-octene After replacing the inside of a dry 1-liter polymerization reactor equipped with a stirrer with dry argon, 420 ml of dry n-hexane and 60 ml of 1-octene were charged, and 15
The temperature was raised to 0 ° C. 20 ml of dry n-hexane, 1.0 ml of a hexane solution of triisobutylaluminum (1.0 mol / l) were placed in a catalyst introduction tube,
10 ml (20 μmol-Ti) of the above three-component contact reaction product was charged and introduced into the polymerization reactor simultaneously with ethylene gas. Polymerization was carried out at 150 ° C. for 5 minutes while supplying ethylene gas so that the ethylene partial pressure was maintained at 24 kg / cm ² G, and the following operation was carried out in the same manner as in Example 1. 3.5 g of an ethylene-octene copolymer having a melting point of 118 ° C. was obtained. [Η] of the obtained polymer was 5.2 (deciliter /
g).

Example 4 (1) Copolymerization of ethylene and 1-octene A dry 1 L polymerization reactor equipped with a stirrer was purged with dry argon, and then 420 mL of dry toluene and 60 mL of 1-octene were charged. , 150
The temperature was raised to ° C. Dry toluene 20
Milliliter, 1.0 ml of hexane solution of triisobutylaluminum (1.0 mol / l), 1.0 ml of toluene dispersion of dimethylanilinium tetra (pentafluorophenyl) borate (0.1 mol / l), tetrachloride Two milliliters of a hexane dispersion of zirconium (30 mmol / L) was charged and introduced into the polymerization reactor simultaneously with ethylene gas. Ethylene partial pressure 2
Polymerization was carried out at 150 ° C. for 5 minutes while supplying ethylene gas so as to maintain the pressure at 4 kg / cm ² G, and the following operation was carried out in the same manner as in Example 1. 2.7 g of an ethylene-octene copolymer having a melting point of 129 ° C. were obtained. (Η) of the obtained polymer is 6.
4 (deciliter / g).

[0040]

As described above, according to the present invention, an ethylene polymer having a low melting point and excellent moldability can be obtained stably and efficiently without using a large amount of organoaluminum. Therefore, the ethylene polymer obtained in the present invention, particularly the linear low-density polyethylene, can be effectively used for films, packaging materials, heat insulating materials, foam materials and the like.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-295021 (JP, A) JP-A-5-310829 (JP, A) JP-A-5-43618 (JP, A) JP-A-2- 169526 (JP, A) Kaminsky, Polymerization and Copolymerization of Ore fines with Metallocene / Aluminoxane Catalysts, Catalyst, Japan, Vol. 33, No. 8, No. 536-541 J. Herwig and W.C. Ka minsky, Halogen-Fre e Soluble Ziegler Catalysts with Met hylaluminoxane as Catalyst, Polymer B ulletin, Vol. 9, 464-469 (58) investigated the field (Int.Cl. ^7, DB name) C08F 4/60 - 4 / 70

Claims (1)

(57) [Claims] In producing ethylene or a copolymer of ethylene with at least one α-olefin and / or a non-conjugated diene as a raw material, (a) any one of the general formulas (I) to (IV) may be used as a catalyst. periodic table group IVB transition metal compound represented by either also general formula (VI) to form an ionic complex by reacting with (b) the transition metal compound
Is an ethylene polymer characterized by being polymerized or copolymerized at a temperature higher than the melting point of the ethylene polymer to be produced, using the compound represented by the formula (VII) and the organoaluminum compound (c) as main components. Manufacturing method. _{^{CpMR 1 a R 2 b R 3}} c ··· (I) Cp 2 MR 1 a R 2 b ··· (II) (Cp-A e -Cp) MR 1 a R 1 b ··· (III) MR ¹ _a R ² _b R ³ _c R ⁴ _d (IV) (where M is zirconium, titanium or hafnium
At least one IVB transition gold selected from the periodic table
Genus, Cp is a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group.
R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen group
Independently represents a σ-binding ligand or Lewis base;
They can be the same or different
No. A represents a covalent cross-link, and e represents an integer of 0 to 6.
Indicates a number. ) ([L ¹ -R ^{7] k} +) _p ^{([M 3 Z 1 Z 2 ·· Z} n ] ^(nm) _-) q · · · (VI) ([L ^{2] k} +) _p ([M ⁴ Z ¹ Z ² ·· Z ^{n] _{(nm) -) q ··· (}} VII) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 3 C or R
¹¹ M is ⁶⁾ (wherein, L ¹ is a Lewis base, M ³ and M ⁴ are each
VB, VIB, VIIB, VIII, IB, II of the periodic table
An element selected from Group B, IIIA, IVA and VA;
An element selected from the group IIIA, IVA and VA,
Group IIIB M ⁵ and M ^6, respectively Periodic Table, IVB group,
VB, VIB, VIIB, VIII, IA, IB, IIA
Group, an element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ
Represents a hydrogen atom, a dialkylamino group, and a
20 alkoxy groups, aryloxy having 6 to 20 carbon atoms
Group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms.
Reel group, alkylaryl group, arylalkyl group,
A halogen-substituted hydrocarbon group having 1 to 20 carbon atoms,
20 acyloxy group, organometalloid group or halo gate
Shows the emission atoms, Z ¹ to Z ⁿ may bind two or more thereof with each other
To form a ring. R ⁷ is a hydrogen atom, carbon number 1
To 20 alkyl groups, aryl groups having 6 to 20 carbon atoms,
A alkylaryl group or an arylalkyl group;
⁸ and R ⁹ are each a cyclopentadienyl group,
Cyclopentadienyl, indenyl or fluor
An aryl group, R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, aryl
Group, alkylaryl group or arylalkyl group
You. R ¹¹ is tetraphenylporphyrin, phthalocyanine
And macrocyclic ligands such as m is the valence of M ³ or M ⁴
Is an integer of 1 to 7, n is an integer of 2 to 8, and k is [L ¹ −
R ⁷ ] and [L ² ] are ionic valences and are integers of 1 to 7;
The above integer, q = (p × k) / (nm). )