JP2000128931A - Ethylene/alpha-olefin copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene/α-olefin copolymer having a high molecular weight showing an excellent effect as a modifier, and to provide a method for producing the copolymer. SOLUTION: This ethylene/α-olefin copolymer comprises a constituent unit derived from ethylene and a constituent unit derived from a 5-20C α-olefin, has 1-39 mol% ethylene constituent unit, 61-99 mol% α-olefin constituent unit, the ratio of a weight-average molecular weight to a number-average molecular weight measured by gel permeation chromatography of 1.8-3.0 and 4-15 dL/g intrinsic viscosity measured at 135 deg.C in decalin. The ethylene/α-olefin copolymer is obtained by copolymerizing the constituent units by an olefin polymerization catalyst composed of (A) a transition metal compound and at least one compound selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound and (B-3) a compound to form an ion pair by a reaction with the transition metal compound (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ethylene / α-olefin copolymer and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, amorphous ethylene / α-
Olefin copolymers have excellent heat resistance, weather resistance, and low-temperature properties, and are widely used as modifiers for various structural materials. Among them, copolymers composed of α-olefins having 5 or more carbon atoms are particularly excellent in anti-vibration properties and exhibit excellent reforming effects.

As a catalyst for producing an ethylene / α-olefin copolymer, a titanium catalyst comprising a titanium compound and an organoaluminum compound and a vanadium catalyst comprising a vanadium compound and an organoaluminum compound are known. . The copolymer obtained from the titanium-based catalyst has a problem that the composition distribution and the molecular weight distribution are wide and the low-temperature characteristics and the mechanical characteristics are poor. On the other hand, with a vanadium-based catalyst, it is difficult to obtain a copolymer having a sufficient content of α-olefin in copolymerization of ethylene with α-olefin having 5 or more carbon atoms.

Further, as a catalyst capable of producing an olefin polymer with high polymerization activity, a catalyst system comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) or an ionized ionic compound is known. JP-A-9-183817 discloses a copolymer having a relatively high content of α-olefins having 5 or more carbon atoms by a catalyst system comprising a specific metallocene compound and an ionized ionic compound, and a method for producing the same. However, in this method, both the content and the molecular weight of the α-olefin are not sufficient to improve the vibration damping properties of the material.

[0005] Japanese Patent Application No. 9-1099 filed by the present applicant.
No. 18 discloses a method for producing an ethylene / α-olefin copolymer containing a sufficiently large amount of α-olefin having 5 or more carbon atoms using a transition metal complex catalyst having a titanium-amide bond. However, for higher performance, a polymer having a higher molecular weight has been desired.

[0006]

An object of the present invention is to provide an ethylene / α-olefin copolymer having a high molecular weight and exhibiting an excellent effect as a modifier, which has been made in view of the prior art as described above, and an ethylene / α-olefin copolymer. It is intended to provide a manufacturing method.

[0007]

SUMMARY OF THE INVENTION The ethylene / α-olefin copolymer according to the present invention has a constitutional unit derived from ethylene and a carbon number of 5 to 5.
Consisting of 20 structural units derived from α-olefin,
(A) Constituent units derived from ethylene are 1 to 39 mol
%, Structural unit derived from α-olefin is 61 to 99 m
(b) weight average molecular weight (M) measured by gel permeation chromatography (GPC).
w) and the number average molecular weight (Mn) ratio (Mw / Mn) is 1.
8 to 3.0, and (c) the intrinsic viscosity [η] measured in 135 ° C decalin is 4 to 15 dl / g.

Further, the ethylene / α-olefin copolymer according to the present invention has a content in the polymer measured by ¹³ C-NMR.
The proportion of-(CH ₂ ) ₂ -chains is 1 mol% in terms of ethylene
It is preferably at least 30 mol%.

The method for producing an ethylene / α-olefin copolymer according to the present invention comprises: (A) a transition metal compound represented by the following general formula (I); (B) an (B-1) organometallic compound; (B
-2) with an organoaluminum oxy compound and (B-3) an olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds which react with the transition metal compound (A) to form an ion pair; 5-20 carbon atoms
Α-olefin is copolymerized.

[0010]

Embedded image (In the above formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and may be a hydrogen atom. , A halogen atom,
A hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, of which Two or more of them may be connected to each other to form a ring, and when m is 2 or more, one group of R ^{1 to} R ⁶ of one ligand and another group may optionally one radical of R ¹ to R ⁶ of the ligands are linked, R ¹ each other between each ligand, R ² together, R ³ together, R ⁴ together, R ⁵ each other,
R ⁶ may be the same or different from each other, and n is
X is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group. Represents a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group,
When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring. )

[0011]

DETAILED DESCRIPTION OF THE INVENTION The ethylene / α-olefin copolymer according to the present invention and the method for producing the ethylene / α-olefin copolymer will be specifically described below.

The ethylene / α-olefin copolymer according to the present invention has a constitutional unit derived from ethylene and has 5 to 20 carbon atoms.
Is a copolymer consisting of structural units derived from α-olefins. Examples of the α-olefin having 5 to 20 carbon atoms used in the present invention include 1-pentene and 3-methyl-1
-Butene, 1-hexene, 4-methyl-1-pentene,
4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Eicosene, etc., and one or more of these are used. Among these, 1-hexene, 1-octene and 1-decene are particularly preferred.

The content of α-olefin in the ethylene / α-olefin copolymer of the present invention measured by ¹³ C-NMR is 61 to 99 mol%, preferably 61 to 90 mol%.
mol%, particularly preferably 62 to 88 mol%.

[0014] ¹³ C-NMR shows that in a sample tube, an ethylene / α-olefin copolymer is completely dissolved in ortho-dichlorobenzene containing a small amount of deuterated benzene as a lock solvent, and then protonated at 120 ° C. It is measured by the complete decoupling method. The chemical shift was set such that the carbon peak of deuterated benzene was 128.0 ppm based on tetramethylsilane, and the other carbon peaks were based on this.

The ethylene / α-olefin copolymer of the present invention is obtained by gel permeation chromatography (GP
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured according to C) is in the range of 1.8 to 3.0, preferably 1.9 to 2.5.

Intrinsic viscosity ([η]) of the ethylene / α-olefin copolymer of the present invention measured in decalin at 135 ° C.
Is 4 dl / g ≦ [η] ≦ 15 dl / g, preferably 5 dl / g ≦ [η] ≦ 12, more preferably 6 dl / g
/ G ≦ [η] ≦ 10 dl / g.

Further, in the ethylene / α-olefin copolymer of the present invention,-in the total polymer measured by ¹³ C-NMR was used.
The proportion of (CH ₂ ) ₂ -chain is 1 mol in terms of ethylene
% To 30 mol%, preferably 5 mol%.
Not less than 30 mol%.

Here, the — (CH ₂ ) ₂ — chain present in the ethylene / α-olefin copolymer will be described. The existing ethylene / α-olefin copolymer has the following structure (II)
have. When the α-olefin is polymerized with ethylene at random and with good regioregularity, for example, always with 1,2-insertion, the value of n of (CH ₂ ) _{n in} the polymer chain is n
= 1, 3, 5,..., And there is no chain (CH ₂ ) _{2 with} n = 2.

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On the other hand, the ethylene / α-olefin copolymer of the present invention contains α-olefin units (A) inserted at irregular positions (eg, 1,1-insertion versus 2,1-insertion). To form a chain (CH ₂ ) ₂
Having the following structure (III):

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In the case where α-olefin (A) is inserted at 2, 1 after ethylene is inserted, n-linked chain (B) derived from ethylene inserted immediately before, ie,-(CH ₂ ) ₂ -chain is observed. it can. Subsequently, the α-olefin (D) is
When inserted, a chain (C) of n = 2 derived from α-olefin, that is, a — (CH ₂ ) ₂ — chain is observed. That is, the — (CH ₂ ) ₂ — linkage is observed when the α-olefin inserts randomly. This-(CH ₂ ) ₂ -linked carbon is generally called αβ carbon, and the signal of the αβ carbon is ¹³
It shows a peak around 30.5 to 32.5 ppm by C-NMR measurement. From the signal intensity at this position, the amount of ethylene chains in the polymer structure can be quantified.

It is known that, in conventional ethylene / α-olefin copolymers obtained from titanium-based catalysts and metallocene catalysts, α-olefins are intercalated with 1,2 with good regioregularity. (CH ₂ ) ₂ -chains cannot be observed. Further, in the vanadium-based catalyst, since the α-olefin is inserted into the resulting polymer at a high regioregularity,-(CH ₂ ) ₂ -chains cannot be observed in the same manner as described above. As in the present invention, a copolymer of ethylene and an α-olefin having 5 or more carbon atoms, in which a — (CH ₂ ) ₂ — chain is observed, has an excellent modifying effect in terms of transparency, impact resistance, and the like. Show.

The ethylene / α-olefin copolymer of the present invention comprises (A) a transition metal compound represented by the following general formula (I), (B) an organometallic compound (B-1), and (B-2) Ethylene) in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of an organoaluminum oxy compound and (B-3) a compound which forms an ion pair by reacting with the transition metal compound (A). And an α-olefin having 5 to 20 carbon atoms.

Hereinafter, each catalyst component forming the olefin polymerization catalyst of the present invention will be described.

(A) Transition Metal Compound The transition metal compound used in the present invention is represented by the following general formula (I).

Embedded image (N ... M in the above formula generally indicates coordination, but in the present invention, coordination may or may not be performed.)

In the general formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 includes lanthanoids), and preferably Group 3 to Group 9 (Group 3 includes lanthanoids). ), More preferably a metal atom of groups 3 to 5 and 9, and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, Hafnium, vanadium,
Niobium, tantalum, cobalt, rhodium and the like, more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium and tantalum, and particularly preferably titanium, zirconium and hafnium.

M represents an integer of 1 to 6, preferably 1 to 4. R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
It indicates a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.

Here, the halogen atom includes fluorine,
Chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like.
30, preferably 1 to 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; A straight-chain or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; and 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl, preferably 3 to 20 cyclic saturated hydrocarbon groups; cyclopentadienyl, indenyl,
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as fluorenyl; an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl; tolyl And alkyl-substituted aryl groups such as iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl and the like.

In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon having 1 to 30, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group. The hydrocarbon group may be substituted with another hydrocarbon group, for example, an aryl-substituted alkyl group such as benzyl and cumyl.

Further, the hydrocarbon group may be a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic anhydride. Oxygen-containing groups such as groups; amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, amino groups A boron-containing group such as a boranediyl group, a borantoriyl group, a diboranyl group, etc .; a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group;
A sulfur-containing group such as a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group; It may have a phosphorus-containing group such as a phosphoryl group, a thiophosphoryl group, a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Of these, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, t-butyl, neopentyl, n-hexyl and other linear or branched alkyl groups having 1 to 30, preferably 1 to 20 carbon atoms; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like. Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 6 to 30 carbon atoms, Preferably, 6 to 20 substituents such as an aryl group or an aryloxy group have 1 to 5 substituents.
A monosubstituted substituted aryl group is preferred.

Examples of the heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran;
Residues such as sulfur-containing compounds such as thiophene, and groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms. Is mentioned.

Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, and phosphorus-containing group represented by R ^{1 to} R ⁶ are the same as those exemplified above.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and diphenylmethyl. Silyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy. Examples of the germanium-containing group and the tin-containing group include those in which silicon of the silicon-containing group is replaced with germanium and tin.

Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically. Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy,
Isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, aryloxy groups include phenoxy,
2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, as an acyl group, formyl group, acetyl group,
Preferred examples include a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group, and examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl.

Among the nitrogen-containing groups, amide groups include acetamido, N-methylacetamido, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include: Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Among the sulfur-containing groups, alkylthio groups include methylthio, ethylthio, etc., arylthio groups include phenylthio, methylphenylthio, naltylthio, etc., and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthio groups. Carbonyl and the like, and sulfonate groups such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate; Are preferred.

Preferably, R ⁶ is a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. Group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, and more preferably a halogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group. Preferably, there is.

Preferred hydrocarbon groups for R ⁶ include:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. having 1 to 30, preferably 1 to 20 linear or branched carbon atoms Alkyl group; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl and triphenylyl An aryl group having 6 to 30, preferably 6 to 20; and an alkyl or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms in these groups, and having 1 to 30, preferably 1 to 30 carbon atoms. Is a halogenated alkyl group of 1 to 20, having 6 to 30 carbon atoms, preferably 6 to 2 carbon atoms.
A group further substituted with a substituent such as an aryl group or an aryloxy group of 0, a halogen, a cyano group, a nitro group, a hydroxy group and the like are preferable.

Preferred hydrocarbon-substituted silyl groups for R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, as R ⁶ , particularly, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl and the like having 3 to 30, preferably 3 to 2 carbon atoms.
A branched alkyl group of 0, a group in which a hydrogen atom of these groups is substituted with an aryl group having 6 to 30, preferably 6 to 20 carbon atoms (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl or the like having 3 to 30, preferably 3 to 2 carbon atoms.
0 is preferably a group selected from cyclic saturated hydrocarbon groups, or phenyl, naphthyl, fluorenyl,
6 to 3 carbon atoms such as anthranil and phenanthryl
It is also preferably 0, preferably 6 to 20 aryl groups or hydrocarbon-substituted silyl groups.

R ^{1 to} R ⁶ are two or more of these groups, preferably adjacent groups are linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

Further, when m is 2 or greater, and one of the radicals R ¹ to R ⁶ of one of the ligands, R ¹ ~ other ligands
One group of R ⁶ may be linked. Further, when m is 2 or more, R ¹ and R ² between each ligand,
R ³ together, R ⁴ together, R ⁵ each other, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 3.
Is an integer. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing residue. Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

Here, as the halogen atom, fluorine,
Chlorine, bromine and iodine. Examples of the hydrocarbon group include the same groups as those described above for R ^{1 to} R ⁶ . Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; and those having 3 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl
To 30 cycloalkyl groups; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl;
Examples include, but are not limited to, aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl. In addition, these hydrocarbon groups include halogenated hydrocarbons, specifically, having 1 to 2 carbon atoms.
A group in which at least one hydrogen atom of the hydrocarbon group 0 is substituted with a halogen is also included. Among them, the number of carbon atoms is 1 to
Twenty are preferred.

As the heterocyclic compound residue, R ¹
It includes the same as those exemplified in to R ^6.

Examples of the oxygen-containing group include the same groups as those exemplified for R ^{1 to} R ⁶ above. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; a phenoxy group and a methyl group. Aryloxy groups such as phenoxy, dimethylphenoxy and naphthoxy;
Arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups, and the like, but are not limited thereto.

Examples of the sulfur-containing group include the same as those exemplified above for R ^{1 to} R ⁶ , and specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate and the like. Sulfonate groups such as phonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfate Sulfonate groups such as carboxylate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate; alkylthio; arylthio; and the like, but are not limited thereto. .

Specific examples of the nitrogen-containing group include the aforementioned R ¹ to
The same ones as those exemplified for R ⁶ can be mentioned, and specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino , Ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group.
It is not limited to these.

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triphenylphosphine;
Triarylphosphine groups such as tolylphosphine; phosphite groups (phosphide groups) such as methyl phosphite, ethyl phosphite and phenyl phosphite; phosphonic acid groups; phosphinic acid groups, and the like, but are not limited thereto. is not.

Specific examples of the silicon-containing group include the aforementioned R ¹
It includes the same ones as exemplified to R ^6, specifically, phenyl silyl, diphenyl silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl silyl, triphenyl silyl, methyl diphenyl silyl, tritolylsilyl A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same groups as those exemplified in the above R ^{1 to} R ⁶ , and specific examples include a group in which silicon of the silicon-containing group is replaced with germanium. .

Specific examples of the tin-containing group include the aforementioned R ¹ to
The same groups as those exemplified for R ⁶ can be mentioned, and more specifically, a group in which silicon of the silicon-containing group is substituted with tin is mentioned.

Specific examples of the halogen-containing group include P
Examples include, but are not limited to, fluorine-containing groups such as F ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ .

Specific examples of the aluminum-containing group include A
lR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like), but is not limited thereto.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other.
May be bonded to each other to form a ring.

Hereinafter, specific examples of the transition metal compound represented by the general formula (I) will be shown, but the invention is not limited thereto. In the following specific examples, M is a transition metal element, and is individually Sc (III), Ti (III), Ti (III).
(IV), Zr (III), Zr (IV), Hf (IV), V (IV), Nb
(V), Ta (V), Co (II), Co (III), Rh (II), R
h (III) and Rh (IV) are shown, but not limited thereto. Among these, Ti (IV), Zr (IV), H
f (IV) is preferred, and Ti (IV) is particularly preferred.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different. n is determined by the valence of the metal M. For example, when two monoanion species are bonded to a metal, n = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. . For example, when the metal is Ti (IV), n = 2, when Zr (IV), n = 2, and when Hf (IV), n = 2.

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

Embedded image In the above examples, Me is a methyl group, Et is an ethyl group,
iPr is i-propyl group, tBu is tert-butyl group, Ph
Represents a phenyl group.

The transition metal compound (A) represented by the general formula (I) includes a transition metal compound represented by the following general formula (Ib).

Embedded image (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, and a heterocyclic compound. Residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
Or more may be connected to each other to form a ring;
Is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, and a halogen atom. A containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; A plurality of groups represented by X may be bonded to each other to form a ring, and Y is at least one selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron. A divalent linking group containing a species element is shown. )

In the general formula (Ib), at least one of R ^{6 and} R ¹⁰ , particularly both, are a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
It is preferably a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

In formula (Ib), M, R ^{1 to} R ¹⁰ and X can be the same groups as M, R ^{1 to} R ⁶ and X described for the compound of formula (I).

X is particularly preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group. When n is 2 or more, the ring formed by linking two or more Xs to each other may be an aromatic ring or an aliphatic ring.

Y represents a divalent linking group containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron. These bonding groups Y preferably have a structure in which the main chain is composed of 3 or more atoms, more preferably 4 or more and 20 or less, and particularly preferably 4 or more and 10 or less. In addition, these bonding groups may have a substituent.

As the divalent linking group (Y), specifically,
A chalcogen atom such as O-, -S-, -Se-; -NH
-, -N (CH ₃ )-, -PH-, -P (CH ₃ )-and other nitrogen or phosphorus atom-containing groups; -SiH _2- , -Si (C
A silicon atom-containing group such as H ₃ ) _2- ; -SnH _2- , -Sn
(CH _{3) 2} - tin atom-containing groups such as; -BH -, - B
And a boron atom-containing group such as (CH ₃ ) — and —BF—. The hydrocarbon group is not particularly limited, but may be-(CH
_{2) 4 -, - (CH} 2) 5 -, - (CH 2) 6 - saturated hydrocarbon group having 3 to 20 carbon atoms such as, cyclohexylidene group, a cyclic saturated hydrocarbon group such as cyclohexylene group A part of these saturated hydrocarbon groups is a hydrocarbon group of 1 to 10, fluorine, chlorine, halogen such as bromine, oxygen, sulfur,
Groups substituted by hetero atoms such as nitrogen, phosphorus, silicon, selenium, tin and boron; residues of cyclic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene and anthracene; pyridine, quinoline, thiophene and furan And the like, the residue of a cyclic compound having 3 to 20 carbon atoms including a hetero atom.

The following are specific examples of the transition metal compound represented by the above general formula (Ib), but the invention is not limited thereto.

[0073]

Embedded image

[0074]

Embedded image In the above examples, Me represents a methyl group, and Ph represents a phenyl group.

In the present invention, a transition metal compound in which titanium metal is replaced with a metal other than titanium such as zirconium or hafnium in the above compounds may be used.

(B-1) Organometallic Compound As the (B-1) organometallic compound used in the present invention, specifically, the following Periodic Groups 1, 2 and 12, 1
A group 3 organometallic compound is used.

[0077] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3 and m + n + p + q = 3. The organoaluminum compound represented by).

[0078] (B-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a metal belonging to Group 1 of the periodic table and aluminum.

(B-1c) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

As the organoaluminum compound belonging to the above (B-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by

[0081] formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

More specifically, the organoaluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum;

Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z
(Where x, y, and z are positive numbers and z ≧ 2x), and a trialkenyl aluminum such as triisoprenyl aluminum;

Alkyl aluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide and butyl Alkyl aluminum sesquialkoxides such as aluminum sesquibutoxide;

Partially alkoxylated alkyl aluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _{0.5 and the} like; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4- Methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-)
Methylphenoxide), diisobutylaluminum (2,
Dialkylaluminum aryloxides such as 6-di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutyl Dialkylaluminum halides such as aluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide Partially halogenated alkyl aluminums, such as the alkyl aluminum dihalides of

Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxychloride, butyl Partially alkoxylated and halogenated alkyl aluminums such as aluminum butoxycyclolide and ethyl aluminum ethoxy bromide can be mentioned.

Further, a compound similar to (B-1a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
(C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

As the compound belonging to the above (B-1b), Li
Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified.

In addition, (B-1) organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyl lithium, or a combination of aluminum halide and alkyl magnesium can also be used.

(B-1) Among the organometallic compounds, an organoaluminum compound is preferred. The above-mentioned (B-1) organometallic compounds are used alone or in combination of two or more.

(B-2) Organoaluminum oxy compound The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. May be a benzene-insoluble organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound.

(2) In a medium such as benzene, toluene, ethyl ether or tetrahydrofuran, an organic aluminum compound such as trialkyl aluminum is directly added to water,
A method of applying ice or water vapor. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include the compounds (C-1a)
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.
Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Certain, ie, those that are insoluble or poorly soluble in benzene, are preferred.

Examples of the organoaluminum oxy compound used in the present invention include a boron-containing organoaluminum oxy compound represented by the following general formula (i).

Embedded image

In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other.

The organoaluminum oxy compound containing boron represented by the general formula (i) is represented by the following general formula (ii)
And R ²⁰ —B— (OH) ₂ ... (Ii) (wherein R ²⁰ represents the same group as above) under an inert gas atmosphere. In an inert solvent,
It can be produced by reacting at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (ii) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid include those described in (B-1a) above.
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned (B-2) organoaluminum oxy compounds are used alone or in combination of two or more.

(B-3) Reaction with transition metal compound (A)
Compound that forms an ion pair The compound (B-3) that forms an ion pair by reacting with the transition metal compound (A) used in the present invention (hereinafter referred to as “ionized ionic compound”) is the transition metal compound. (A)
Is a compound that reacts with to form an ion pair. Therefore,
Those which form an ion pair by contacting at least the transition metal compound (A) are included in this compound. Examples of such compounds include JP-A-1-501950,
JP-A-1-502036, JP-A-3-17900
No. 5, JP-A-3-179006, JP-A-3-179006
207703, JP-A-3-207704,
Lewis acids described in USP-5321106 and the like,
Examples include ionic compounds, borane compounds and carborane compounds. Furthermore, a heteropoly compound and an isopoly compound can also be mentioned.

Specifically, examples of the Lewis acid include BR
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group or a trifluoromethyl group or fluorine.), For example, trifluoroboron, triphenylboron , Tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o -Tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include a compound represented by the following general formula (VI).

Embedded image In the formula, R ²² includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{23 to} R ²⁶ are an organic group which may be the same or different, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. Specifically, as the ammonium cation, a trimethylammonium cation,
Trialkylammonium cations such as triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- 2,4,
N, N-dialkylanilinium cations such as 6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation;

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ²² , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Dialkylammonium salts, triarylphosphonium salts and the like are also included.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VII) or (VIII) are also included.

[0115]

Embedded image (In the formula, Et represents an ethyl group.)

Embedded image

Specific examples of the borane compound include, for example, decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride-1,3-dimethyl-1,3-dicarbanona borane, 7,8-dicarban Decaborane (13),
2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n -Butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1- Carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl
Butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium
7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (1
2), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl
Butyl) ammonium undecahydride-8-ethyl
-7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammoniumundecahydride-8-allyl-7 , 9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-4,6-dibromo-7 -Salts of anions such as carbaundecaborates;

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun Decaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecarate) Hydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n -Butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dica Ruboundecaborate) ferrate (III), tri (n-butyl)
Ammonium bis (nonahydride-7,8-dimethyl-
7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [tri ( n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (IV), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaun Decaborate) nickelate (IV)
And the like, and salts of metal carborane anions.

The heteropoly compound is composed of atoms consisting of silicon, phosphorus, titanium, germanium, arsenic or tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdatovantovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, salts of these acids, for example, metals of Group Ia or IIa of the Periodic Table, specifically
Salts with lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like, and organic salts such as triphenylethyl salt, and isopoly compounds can be used,
This is not the case.

The heteropoly compound and isopoly compound are not limited to one of the above compounds, and two or more can be used. The above-mentioned (B-3) ionized ionic compound is used alone or in combination of two or more.

FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention.

In the polymerization, the method of use and the order of addition of each component are arbitrarily selected, but the following methods are exemplified. (1) Component (A) and at least one component (B) selected from (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) an ionized ionic compound Simply referred to as "component (B)") in any order. (2) A method in which the component (A), the catalyst component in which the component (B-1) is brought into contact in advance, and the component (B-3) are added to the polymerization reactor in an arbitrary order. (3) A method in which the component (A), the catalyst component in which the component (B-1) is brought into contact in advance, and the components (B-1) and (B-3) are added to the polymerization reactor in any order. In this case, the components (B-1) may be the same or different.

(4) A method of adding the catalyst component in which the component (A), the component (B-1) and the component (B-3) are brought into contact in advance, and the component (B-1) to the polymerization reactor in an arbitrary order. . In this case, the components (B-1) may be the same or different. (5) A method in which the catalyst in which the component (A) and the component (B-2) are brought into contact in advance is added to the polymerization reactor. (6) a catalyst component in which the component (A) and the component (B-2) are brought into contact in advance,
And adding the component (B-1) or (B-2) to the polymerization reactor in any order. In this case, the components (B-2) may be the same or different. Among them, the methods (2), (3) and (4) are particularly preferable.

In the process for producing an ethylene / α-olefin copolymer according to the present invention, for example, olefin copolymerization is carried out by copolymerizing ethylene and α-olefin in a solution in the presence of an olefin polymerization catalyst as described above. Obtain a polymer.

In the present invention, the polymerization can be carried out by a liquid phase polymerization method such as solution polymerization or suspension polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof, and the olefin itself is used as a solvent. You can also.

In conducting the olefin polymerization using the olefin polymerization catalyst as described above, the component (A)
It is used in an amount of usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻³ mol per liter of liquid phase.

The component (B-1) is composed of the component (B-1) and the component (A)
The molar ratio with the transition metal atom (M) in [(B-1) / M] is
Usually 0.01 to 100,000, preferably 0.05 to 5
0000 is used. Component (b-2)
Is a molar ratio [(b-2) / M] between the aluminum atom in the component (b-2) and the transition metal atom (M) in the component (A),
Usually 10 to 500,000, preferably 20 to 10,000
It is used in such an amount that it becomes zero. Component (b-3) is a component
The molar ratio of (b-3) to the transition metal atom (M) in the component (A) [(b-3) / M] is usually 1 to 10, preferably 1
It is used in such an amount as to be ５5.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually from -50 to +200.
° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to
Under a condition of 50 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the component (B) used.

The transparency and impact resistance can be improved by blending the ethylene / α-olefin copolymer according to the present invention with, for example, polypropylene as a resin modifier.

Further, the ethylene / α-olefin copolymer according to the present invention may contain an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, and the like as long as the object of the present invention is not impaired.
UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, foam inhibitors, crosslinking agents, crosslinking aids, crosslinking accelerators, In addition to additives such as flowability improvers such as peroxides, weld strength improvers, processing aids, weathering stabilizers, blooming inhibitors, etc., if necessary, other polyolefin polymers such as homopolymers such as polyethylene and polypropylene And other α-olefin copolymers and the like may be added. These optional additives and other polyolefin-based polymers may be used in combination of two or more.

[0132]

The ethylene / α-olefin copolymer according to the present invention has a high α-olefin content, a high molecular weight and a narrow molecular weight distribution, and exhibits an excellent modifying effect.

[0133]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In this example, the intrinsic viscosity ([η])
Was measured in decalin at 135 ° C. Molecular weight distribution (M
w / Mn) was measured as follows using GPC-150 manufactured by Millipore. The separation column is TSK GNH
HT, the column size is 27 mm in diameter and 60 in length
0 nm, the column temperature was 140 ° C., and the mobile phase was
o-Dichlorobenzene (Wako Pure Chemical) and B as an antioxidant
HT (Takeda Pharmaceutical) 0.025% by weight, 1.0 ml /
The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene manufactured by Tosoh Corporation was used. The amount of — (CH ₂ ) ₂ — chains in the polymer was determined by ¹³ C-NMR
By measurement, it was quantified by the signal intensity of a peak around 30.5 to 32.5 ppm.

Example 1 200 m sufficiently purged with nitrogen
To the 1 reactor, 60 ml of heptane and 40 ml of 1-hexene were added, and ethylene was passed at a rate of 10 liter / h, and the mixture was heated at 25 ° C.
With stirring. Then triisobutylaluminum 0.1
After the addition of 25 mmol, 0.05 mmol of triisobutylaluminum previously mixed, 0.005 mmol of the following compound 1 and 0.1 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate.
A 006 mmol solution was added to initiate polymerization. 25 ° C
, And the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added little by little to 1 liter of acetone to precipitate a polymer, separated from the solvent, and dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / hexene copolymer weighed 1.49 g,
The hexene content measured by H ¹ -NMR was 68.1 mol.
%, The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is Mw / Mn = 2.12, the intrinsic viscosity [η] is 6.51 dl / g, and-(CH ₂ ) ₂ -Linkage was 16.6 mol%.

Embedded image

Example 2 The flow rate of ethylene during polymerization was 5
Polymerization was carried out in the same manner as in Example 1 except that the amount was changed to liter / h. The resulting ethylene / hexene copolymer was 1.06
g, and the hexene content measured by ¹ H-NMR is 8
4.8 mol%, weight average molecular weight (M
w) and number average molecular weight (Mn) ratio Mw / Mn = 2.1
0, intrinsic viscosity [η] is 5.64 dl / g, −
The amount of (CH ₂ ) ₂ -chain was 20.5 mol%.

Example 3 Polymerization was carried out in the same manner as in Example 1 except that 1-hexene was changed to 1-octene. The obtained ethylene / octene copolymer weighed 1.44 g,
Octene content measured by ¹ H-NMR is 72.8 mol.
%, The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC = 2.18, the intrinsic viscosity [η] is 5.95 dl / g, and-(CH ₂ ) in the polymer. _{The 2} -chain content was 17.1 mol%.

[Brief description of the drawings]

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

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture F-term in Mitsui Chemicals, Inc. (reference) 4J028 AA01A AB00A AB01A AC01A AC10A AC20A AC28A AC29A AC31A AC39A AC45A AC47A AC49A BA00A BA01B BA02B BA03B BB00A BB01B BB02B BC01B BC03B BC05B BC09B BC12B BC13B BC15B BC16B BC17B BC18B BC24B BC25B EB02 EB07 FA02 FA03 GA04 GA06 GA18 GB01 4A100 AAP09AAA

Claims (3)

[Claims] 1. A structural unit derived from ethylene and having 5 carbon atoms
Consisting of structural units derived from α-olefins of from 20 to 20,
(A) Constituent units derived from ethylene are 1 to 39 mol
%, The structural unit derived from the α-olefin is 61 to 99%
(b) the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.8 to 3.0, (C) An ethylene / α-olefin copolymer having an intrinsic viscosity [η] of 4 to 15 dl / g measured in decalin at 135 ° C. 2. A structural unit derived from ethylene and having 5 carbon atoms.
Comprising structural units derived from α-olefins of from 20 to 20,
(A) Constituent units derived from ethylene are 1 to 39 mol
%, The structural unit derived from the α-olefin is 61 to 99%
(b) the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.8 to 3.0, (C) the intrinsic viscosity [η] measured in decalin at 135 ° C. is 4 to 15 dl / g,
(D) — (CH ₂ ) ₂ — in the polymer measured by ¹³ C-NMR
The chain ratio is 1 mol% or more and 30 m in terms of ethylene.
ol% or less, ethylene / α-olefin copolymer. (A) a transition metal compound represented by the following general formula (I), (B) an organometallic compound (B-1), (B-2) an organoaluminum oxy compound, and (B-3) Transition metal compound
(A) is reacted with an olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds forming an ion pair to form ethylene and α-
3. The method for producing an ethylene / α-olefin copolymer according to claim 1, wherein the olefin is copolymerized. Embedded image (In the above formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and may be a hydrogen atom. , A halogen atom,
A hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, of which Two or more of them may be connected to each other to form a ring, and when m is 2 or more, one group of R ^{1 to} R ⁶ of one ligand and another group may optionally one radical of R ¹ to R ⁶ of the ligands are linked, R ¹ each other between each ligand, R ² together, R ³ together, R ⁴ together, R ⁵ each other,
R ⁶ may be the same or different from each other, and n is
X is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group. Represents a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group,
When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring. )