JP3255710B2 - Method for producing olefin polymer and olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymer .
The present invention relates to a production method and an olefin polymerization catalyst. More specifically, a method for producing an olefin polymer useful in the field of producing products by extrusion, injection molding, thermoforming, rotational molding, etc.
Process and olefin polymerization catalyst .

[0002]

2. Description of the Related Art Conventionally, a method for producing an olefin-based polymer has been based on a combination of a cation catalyst (a combination of a transition metal compound and a so-called ionizing agent which reacts with the transition metal compound to form an ionic complex) with an organoaluminum. The use of a compound is disclosed. (For example, see Japanese Patent Laid-Open No. 3-1
24706, JP-A-3-207704, International application WO9
114713 and WO9207233)

[0003]

However, the above-mentioned production method is characterized in that the activity is improved by using an organoaluminum compound as a role of an alkylating agent or a scavenger, and there is no disclosure of adjusting the molecular weight. .

The present invention has been made in view of the above circumstances, and can control the molecular weight while controlling the decrease in the activity and the increase in the molecular weight distribution, and has a small distribution of the low molecular weight region and the high molecular weight region. It is an object of the present invention to provide a method for producing an olefin polymer having a large molecular weight distribution.

[0005]

In order to achieve the above object, the present invention provides a method for homopolymerizing or copolymerizing an olefin using a catalyst containing the following compounds (A), (B) and (C) as main components. Provided is a method for producing an olefin polymer for performing polymerization. (A) a transition metal compound containing a IVB group tetravalent transition metal (B) a compound which reacts with the above compound (A) to form an ionic complex (C) at least two or more kinds of organoaluminum compounds Provided is a method for producing an olefin polymer in which polymerization is carried out simultaneously using at least two or more kinds of organoaluminum compounds as a catalyst component (C). Further, the present invention provides a method for producing an olefin-based polymer in which at least two or more kinds of organoaluminum compounds as the catalyst component (C) are polymerized in a multi-step polymerization step. Further, the present invention provides a method for producing an olefin-based polymer using a different type of catalyst component (C) in each stage of the multistage process. Furthermore, the present invention provides an olefin polymerization catalyst comprising the catalyst components (A), (B) and (C).

Hereinafter, the present invention will be described in more detail.
FIG. 1 shows a flowchart of the manufacturing method of the present invention.
In the present invention, the compound (A) includes a tetravalent group IVB.
A transition metal compound containing a transition metal is used.

[0007] Such transition metal compounds include periodic
Transition metal selected from group IVB
(Ti), zirconium (Zr) or hafnium (H
f) can be used . In particular, a cyclopentadienyl compound represented by the following general formula (I), (II) or (III) or a derivative thereof, or a compound represented by the following general formula (I
Compounds represented by V) or their derivatives are preferred. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (II
I) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV)

In the formulas (I) to (IV), M ¹ is Ti, Zr
Or Hf atom, Cp is a cyclopentadienyl group,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ are each σ
Ligands such as binding ligands, chelating ligands, and Lewis bases are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, C1-C20 alkoxy groups, C6-C6
Examples of the aryl group include an aryl group, an alkylaryl group or an arylalkyl group having 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples include an acetylacetonate group and a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d
Is an integer of 0 to 4, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2 Amines such as 2,2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene,
Pentadiene, 1-hexene and derivatives thereof; benzene, toluene, xylene,
Examples include cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof. In addition, A in the above formula (III)
Examples of the crosslink by a covalent bond of
Examples include a dimethylmethylene bridge, an ethylene bridge, a 1,1′-cyclohexylene bridge, a dimethylsilylene bridge, a dimethylgermylene bridge, and a dimethylstannylene bridge.

Examples of such compounds include the following and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

The compound of the formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) (Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

Examples of the compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV), for example, the following compounds . Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t -Butylphenoxy) dichlorozirconium, zirconiumbis (acetylacetonate),

Further, in the present invention, the compound (A)
Is a substituted or unsubstituted 2 of the formula (III)
Conjugated cycloalkadienyl groups, provided that at least one
Are substituted cycloalkadienyl groups) in the periodic table
Group IVB transition metal compounds having a polydentate compound bonded to each other via an element selected from Group IVA as a ligand can be suitably used. Examples of such a compound include a compound represented by the following general formula (V) or a derivative thereof.

[0015]

Embedded image Wherein (V), Y is carbon, silicon, germanium or tin ^{_{atom, R 5 t -C 5 H 4}} -t and ^{_{R 5 u -C 5 H 4-}} u are each a substituted cyclopentadienyl group, t And u represent an integer of 1 to 4. Here, R ⁵ represents a hydrogen atom, a silyl group or a hydrocarbon group, which may be the same or different.
Also, at least one cyclopentadienyl ring has
R ⁵ is present on at least one carbon next to the carbon attached to Y. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group. M ² is T
i is a Zr or Hf atom, X is a hydrogen atom, a halogen atom,
It represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, or an alkoxy group having 1 to 20 carbon atoms. Xs may be the same or different, and R ⁶ may be the same or different.

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

[0018]

[0019]

[0020]

[0021]

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the compound may be a group IIIB of the periodic table,
IVB, VB, VIB, VIIB, VIII, IA, IB, II
A cation containing an element selected from Group A, IIB, IVA, and VIIA and a plurality of groups are formed from VB, VIB, and VIIB of the periodic table
A compound comprising an anion bonded to an element selected from Group IV, VIII, IB, IIB, IIIA, IVA and VA, for example, a compound represented by the following formula (VI) or (VII): Can be used. ([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 is ₃ C or R ¹¹ M ⁶⁾

In the formulas (VI) and (VII), L ¹ is a Lewis base, M ³ and M ⁴ are groups VB, VIB and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, V
Group III, IA Group, IB, Group IIA, Group element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 carbon atoms
Aryloxy group having 20 to 20 carbon atoms, 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, 1 to 20 carbon atoms an acyloxy group, an organic metalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7, n is an integer of 2 to 8 and k is an integer of 1 to 7 of an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include 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, amines such as N- dimethylaniline, triethyl phosphine , Triphenyl phosphite
Emissions, phosphines such as diphenyl phosphine, dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, diethyl thioether, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate and the like. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, Sb and the like, preferably B or P, and specific examples of M ⁵ include Li, Na, Ag,
Cu, Br, I, I _3, etc., Mn Specific examples of M ^6, F
e, Co, Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; an aryl group having 6 to 20 carbon atoms,
A phenyl group, p-tolyl group, benzyl group, 4-tert-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 as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5- bis (trifluoromethyl) phenyl group; F, Cl, Br,
I; Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
The same ones as mentioned above can be mentioned. R ⁸ and R
Specific examples of the substituted cyclopentadienyl group ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. (VI),
Among the compounds of the formula (VII), those wherein M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (VI) and (VII), the following compounds can be used particularly preferably. Compound of formula (VI) Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenyltetraborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

[0027]Tetrakis(Pentafluorophenyl) boron
Triethylammonium acid,Tetrakis(Pentafluo
(Phenyl) borate tri (n-butyl) ammonium,Te
Thorakis(Pentafluorophenyl) triphenyl borate
Ammonium,Tetrakis(Pentafluorophenyl)
Tetrabutylammonium borate,Tetrakis(Pentaf
(Fluorophenyl) boric acid (tetraethylammonium),
Tetrakis(Pentafluorophenyl) boric acid (methyl
(N-butyl) ammonium),Tetrakis(Penta
Fluorophenyl) boric acid (benzyl tri (n-butyl)
Ammonium),Tetrakis(Pentafluorophenyl
R) methyldiphenylammonium borate,Tetrakis
(Pentafluorophenyl) borate methyltriphenyla
Nmonium, Tetrakis(Pentafluorophenyl) boron
Dimethyldiphenylammonium acid,Tetrakis(pen
Tafluorophenyl) anilinium borate,Tetrakis
Methylanilinium (pentafluorophenyl) borate,
Tetrakis(Pentafluorophenyl) dimethyl borate
Nilinium,Tetrakis(Pentafluorophenyl) boron
Trimethylanilinium acid,Tetrakis(Pentafluo
Lophenyl) dimethyl borate (m-nitroanilinium)
),Tetrakis(Pentafluorophenyl) boric acid dime
Chill (p-bromoanilinium),

[0028] tetrakis (pentafluorophenyl) borate pyridinium tetrakis (pentafluorophenyl) borate (p- cyanopyridinium) tetrakis (pentafluorophenyl) borate (N- methylpyridinium) tetrakis (pentafluorophenyl) borate (N
-Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p
- cyano -N- methylpyridinium) tetrakis (pentafluorophenyl) borate (p- cyano -N- benzyl pyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium tetrakis (pentafluorophenyl) borate benzyl dimethyl sulfonium tetrakis ( Tetraphenylphosphonium (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis
[3,5-bis (trifluoromethyl) phenyl] dimethylanilinium borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) dimethylanilinium borate, tris (pentafluorophenyl) (p-trifluoro methyl-tetrafluorophenyl) borate triethylammonium tris (pentafluorophenyl) (p-trifluoromethyl-tetrafluorophenyl) borate pyridinium, tris (pentafluorophenyl) (p-trifluoromethyl-tetrafluorophenyl) borate (N- methylpyridinium ) 、 ト
Lis (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (o-cyano-N-
Methylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (p-cyano-N-benzylpyridinium),
Tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) triphenylphosphonium borate, tris (pentafluorophenyl) (2
3,5,6-tetrafluoropyridinyl) dimethylanilinium borate, tris (pentafluorophenyl)
(2,3,5,6-tetrafluoro-pyridinylcarbonyl) borate triethylammonium tris (pentafluorophenyl) (2,3,5,6-tetrafluoro-pyridinylcarbonyl) borate pyridinium, tris (pentafluorophenyl)
(2,3,5,6-tetrafluoropyridinyl) borate (N-methylpyridinium), tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate (o-cyano- N- methylpyridinium), bets
Lis (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate (p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (2,3,5,6-tetrafluoro Pyridinyl) triphenylphosphonium borate, tris (pentafluorophenyl) (phenyl) borate dimethylanilinium ,
Lis (pentafluorophenyl) [3,5-bis (tri
Fluoromethyl) phenyl] borate dimethylanilinium tris (pentafluorophenyl) (4-trifluoromethylphenyl) borate dimethylanilinium, triphenyl (pentafluorophenyl) borate dimethylanilinium, triethylammonium hexafluoroarsenate,

Compound of formula (VII) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (manganese tetraphenylporphyrin), tetrakis
Scan (pentafluorophenyl) borate ferrocenium, Te
Trakis (pentafluorophenyl) borate (1,1′-
Dimethyl ferrocenium), tetrakis (pentafluorophenyl) borate decamethyltetrasiloxane ferrocenium, Tetoraki
Scan (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate formyl ferrocenium tetrakis (pentafluorophenyl) borate cyano ferrocenium tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl ) borate trityl tetrakis (pentafluorophenyl) borate lithium, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride) , Tetra
Kis (pentafluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate,

Compounds other than those of the formulas (VI) and (VII)
For example, tris (pentafluorophenyl) boron, tris
[3,5-bis (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used. One or more compounds that react with the transition metal compound (catalyst component [A]) as the catalyst component [B] to form an ionic complex may be used.

The catalyst component [C] is an organoaluminum compound having at least two or more kinds, and examples of the organic compound include compounds represented by the following general formula (VIII). R ¹² _r AlQ _3-r (VIII) (R ¹² is a hydrocarbon group having 1 to 20, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, Q is a hydrogen atom, Represents an alkoxy group or a halogen atom having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VIII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

In the present invention, these are at least 2
It is necessary to use more than seeds. The combination is not particularly limited, but includes two or more kinds of organoaluminum compounds to be used.
It is preferable to add triisobutylaluminum.
More preferred combinations are triisobutylaluminum and trimethylaluminum, triisobutylaluminum and triethylaluminum, triisobutylaluminum and trimethylaluminum and triethylaluminum. In the case of using step polymerization, two or more steps, a method using different organoaluminum compounds in the former stage and the latter stage, or a method using a combination of the same organoaluminum compound in the former stage and the latter stage may be used if there are two or more types. (For example, they may be combined by changing the use ratio.)

Other compounds of the organoaluminum compound which can be used as the catalyst component [C] include aluminoxanes, which include those represented by the following general formulas (IX) and (X).

Embedded image (R ¹² is the same as in formula (VIII). S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0034]

Embedded image (R ¹² is the same as in formula (VIII). S represents the degree of polymerization, and the number of repeating units is preferably from 3 to 50, and preferably from 7 to 40.) Aluminoxane. Preferred among the compounds of the formulas (IX) and (X) are aluminoxanes having a degree of polymerization of 7 or more.

The method for producing the aluminoxane includes 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 carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

Next, in the present invention, at least one or more of these catalyst components (A), (B) and (C) can be used in contact with the carrier (D). put it here,
The type of the carrier (D) is not limited, and any of an inorganic carrier and an organic carrier can be used, but an inorganic carrier is particularly preferable. Specifically, MgCl ₂ , M
Examples thereof include magnesium compounds such as g (OEt) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ¹³ xX ² y. Here, R13 has 1 to 2 carbon atoms.
0 is an alkyl group, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ² is a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, and y is 0.
~ 2. As the inorganic oxide carrier, SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO ₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite,
Glass fiber and the like can be exemplified. Among these,
SiO ₂ and Al ₂ O ₃ are particularly preferred. The inorganic oxide carrier may contain a small amount of a carbon salt, a nitrate, a sulfate, or the like. Examples of the organic carrier include polymers such as polystyrene, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon. The properties of the carrier (D) used in the present invention vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, causing a decrease in bulk density and clogging of a hopper. The specific surface area of the carrier (D) is usually 1 to 1,0.
00 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.1 to ⁵ cm ³ / g.
It is ^{3 to 3} cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume are, for example, BE
It can be determined from the volume of nitrogen gas adsorbed according to the T method [see "Journal of American Chemical Society", J. Am. Chem. Soc., Vol. 60, p. 309 (1983)]. . Further, it is desirable that the carrier (D) is used after calcining usually at 150 to 1000 ° C, preferably at 200 to 800 ° C. The method for supporting the carrier is not particularly limited, but, for example, generally known methods can be widely used.

Next, in the present invention, the component (E) can be used if necessary. Here, as the component (E), a general formula W—R ¹⁴ — (Q ² ) _m —R ¹⁵ —W ′ (IX) [wherein R ¹⁴ and R ¹⁵ are carbon atoms, as long as the reactivity is not impaired] A C 1 -C 20 hydrocarbon group, a C 7 -C 30 substituted aromatic hydrocarbon group or a C 6 carbon atom having a substituent containing a heteroatom such as oxygen, nitrogen, sulfur, etc.
Represents a substituted aromatic hydrocarbon group having from 40 to 40;
20 hydrocarbon groups, -O-, -S-, -SS-,

Embedded image (R ¹⁶ is a hydrocarbon group having 1 to 6 carbon atoms).
W and W ′ represent a hydroxyl group, an aldehyde group, and a carboxyl group, and m represents an integer of 0 to 5. ] Can be used. Specific examples of the organic compound represented by the general formula (IX) include, for example, 2,2′-dihydroxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylsulfide: 2,2′- Dihydroxy-
3,3'-di-t-butyl-5,5'-dimethylphenyl ether and the like.

Next, the polymerization conditions of the present invention will be described. The catalyst used in the present invention comprises the component (A) and the component (B)
The component and the component (C) are the main components. (A) + (B) +
The component (D) may be added to the component (C). (A) +
The component (E) may be added to the component (B) + (C).
The components (E) and (D) may be added to the components (A) + (B) + (C). The use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.1 to 1: 100, particularly 1: 0.5 to 1:
10, especially 1: 1 to 1: 5. The use temperature is preferably from -100 to 250C. The pressure and time are optional. Component (C) is used in an amount of usually 1 to 2,000 mol, preferably 5 to 5 mol, per 1 mol of component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the molecular weight and the molecular weight distribution can be controlled in addition to the improvement of the polymerization activity. As the component (C), “two or more kinds of organoaluminum compounds” are used. Two or more kinds of organoaluminum compounds may be used simultaneously or stepwise. By simultaneously charging two or more kinds of organoaluminum compounds, the molecular weight can be adjusted while suppressing a decrease in activity and an increase in molecular weight distribution. Furthermore, by gradually charging two or more kinds of organoaluminum compounds, it is possible to obtain a polymer having a large molecular weight distribution in which the distribution of the low molecular weight region and the high molecular region is suppressed. The use ratio of the organoaluminum compound to be used is not particularly limited, and a polymer having various molecular weights and molecular weight distributions can be obtained by variously changing the mixing ratio or the use ratio. As a specific mode of use, triisobutylaluminum: other organoaluminum compound = 1: 9 to 9: 1, preferably 2: 8 to 8: 2.

There is no limitation on the mode of use of the catalyst. For example, (A) and (B), the components may be brought into contact with each other in advance, or the contact product may be separated and washed before use. May be used in contact. Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance.
The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system. However, when the organoaluminum compound in the component (C) is used stepwise, a polymerization system using at least one or more organoaluminum compounds among the components (A), (B) and (C) is preferred. In the later stage, 1 that was not used in the earlier stage
It is preferred to add at least one organoaluminum compound.

When the carrier (D) component is used, the ratio (weight ratio) of the compound (B) to the carrier (D) is 1: 5 to 5: 1.
It is preferably 1: 10000, particularly preferably 1:10 to 1: 500. The ratio (weight ratio) of the compound (A) to the carrier (D) is 1: 5 to 1: 1000, particularly 1:10 to 1:10.
The ratio is preferably set to 1: 500. If the ratio of the compound (B) to the carrier (D) or the mixing ratio of the compound (A) to the carrier (D) is out of the above range, the activity may decrease.

In the present invention, homopolymerization of α-olefin or copolymerization of two or more olefins is carried out in the above polymerization system. In this case, the type of the α-olefin is not particularly limited, but preferably has 2 to 20 carbon atoms. Specifically, ethylene, propylene, 1-butene,
3-methyl-1-butene, 1-hexene, 4-methyl-
1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be suitably used. In the present invention, when two or more α-olefins are copolymerized, the above monomers can be arbitrarily combined, but it is particularly preferable to copolymerize ethylene with an α-olefin having 3 to 10 carbon atoms. The copolymerization ratio of ethylene and an α-olefin having 3 to 10 carbon atoms is
The molar ratio is 99.9: 0.1 to 0.1: 99.9.
In the present invention, in addition to the above-mentioned α-olefin, other unsaturated compounds, for example, vinyl aromatic compounds such as styrene, p-methylstyrene, isopropylstyrene and t-butylstyrene, butadiene, isoprene, 1,5-hexadiene and the like can be used. The copolymerization can be carried out using a small amount of chain diolefins. Also used are cyclic olefins such as norbornene, 1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and cyclic dienes such as ethylidene norbornene and norbornadiene. can do. Usually, the other unsaturated compound is α-
20 mol% or less based on the olefin. in this case,
One or more α-olefins can be preferably used. As the polymerization method, any method such as bulk polymerization, solution polymerization, suspension polymerization, and gas phase polymerization may be used. Further, a batch method or a continuous method may be used. In order to obtain an olefin polymer having a large molecular weight distribution, a step polymerization method is preferred. Here, the step polymerization method means that the organoaluminum compound in the “two or more kinds of organoaluminum compounds” of the catalyst component (C) is charged in at least two or more stages. The time from the initiation of polymerization using the first organoaluminum compound to the introduction of the next different organoaluminum compound is preferably 1 minute or more. The same applies to multiple stages.

Next, the polymerization temperature, monomer / contact ratio, polymerization time and reaction pressure will be described. Regarding the polymerization conditions, the polymerization temperature is -100 to 250 ° C, especially -50 to 20 ° C.
The temperature is preferably set to 0 ° C. The proportion of catalyst corresponding to the reaction raw material, the raw material monomer / component (A) (molar ratio), or the raw material monomer / component (B) (molar ratio) is 1 to 10 ^9, in particular 100 to 10 ⁷ and Preferably. Further, the polymerization time is usually 1 minute to 24 hours, preferably 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg / c.
m ² G, preferably normal pressure to 50 kg / cm ² G. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform, dichloromethane and the like. These solvents may be used alone or in a combination of two or more. Further, monomers such as α-olefins and cyclic olefins may be used as the solvent.

[0043]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, physical properties were measured as follows. Weight average molecular weight (Mw), number average molecular weight (Mn) Using 1,2,4-trichlorobenzene as a solvent, 1
Gel Permeation Chromatography (GPC) at 35 ° C. (Equipment: Waters ALC / GPC
150C, column: TSK HM + GMH manufactured by Tosoh
6 × 2, flow rate: 1.0 ml / min) in terms of polyethylene. Melting point was determined by DSC analysis. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Octene content was measured by ¹ H-NMR.

Example 1 (1) Synthesis of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was mixed with 45 mmol of boron trichloride in hexane. Was reacted to obtain tris (pentafluorophenyl) boron as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of lithium pentafluorophenyl , and lithium tetrakis (pentafluorophenyl) boron was isolated as a white solid. Then, lithium te
By reacting 16 mmol of trakis (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride in water, dimethylanilinium tetrakis (pentafluorophenyl) borate ([PhMe ₂ NH]
[B (C ₆ F ₅ ) ₄ ]) was obtained as a white solid, 11.4 mmol. The fact that the product is the desired product is based on ¹ H-NM
It was confirmed by R, ¹³ C-NMR.

(2) Polymerization of ethylene In a 1 liter autoclave which was dried and replaced with nitrogen, 400 ml of toluene, 0.3 mmol of triisobutylaluminum, 0.3 mmol of trimethylaluminum, 3 μmol of biscyclopentadienyl zirconium dichloride were added. Then, 3 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate obtained in the above (1) was added. Next, at 70 ° C., the pressure in the system was 3 kg.
/ Cm ² , ethylene was continuously supplied to the autoclave and polymerization was carried out for 1 hour. As a result, 42 g of polyethylene was obtained. Mw of the obtained polymer is 16
8,000, Mw / Mn was 2.03.

Example 2 Polymerization of ethylene Polymerization was carried out in the same manner as in Example 1 except that trimethylaluminum was changed to triethylaluminum. As a result, 44 g of polyethylene was obtained. Mw of the obtained polymer was 116,000, Mw / M
n was 2.06. Comparative Example 1 Polymerization of ethylene.
Polymerization was carried out in the same manner as in Example 1 except that 0.6 mmol of triisobutylaluminum was used instead of 0.3 mmol of trimethylluminium, and 47 g of polyethylene was obtained. Mw of the obtained polymer was 255,000, and Mw / Mn was 2.09.

[0047]Example 3 Copolymerization of ethylene and 1-octene 1 liter autoclave dried and purged with nitrogen
, Toluene 400ml, triisobutylaluminum
0.3 mmol, 0.3 mmol of trimethylaluminum
Le,Biscyclopentadienyl zirconium dichloride
3 μmol and obtained in Example 1 (1)Tetrakis
Dimethyl aluminum (pentafluorophenyl) borate
After sequentially adding 3 micromoles, 31 ml of octene was added.
(0.2 mol), and the temperature was raised to 70 ° C.
The partial pressure of styrene is 3kg / cm^TwoEthylene so that
After continuous supply and polymerization for 1 hour, ethylene
-41 g of 1-octene copolymer was obtained. Obtained co
Octene content of polymer is 3 mol%, melt at 190 ° C
Index (MI) is 0.17g / 10min, extreme
The viscosity [η] is 1.73 dl / g, Mw is 139,00
0, Mw / Mn was 1.97, and the melting point was 111.6 ° C.
Was.

Example 4 Copolymerization of ethylene and 1-octene Polymerization was carried out in the same manner as in Example 3 except that trimethylaluminum was changed to triethylaluminum. 4
0 g was obtained. The octene content of the obtained copolymer is 2
Mol%, melt index (MI) at 190 ° C. is 0.48 g / 10 min, intrinsic viscosity [η] is 1.63 d
1 / g, Mw: 124,000, Mw / Mn: 2.0
9. The melting point was 112.9 ° C. Comparative Example 2 Copolymerization of ethylene and 1-octene In Example 3, triisobutylaluminum 0.3
The polymerization was carried out in the same manner as in Example 3 except that 0.6 mmol of triisobutylaluminum was used instead of 0.3 mmol of trimethylaluminum, and an ethylene / 1-octene copolymer was obtained. The octene content of the obtained copolymer was 3 mol%, the melt index (MI) at 190 ° C. was 0.10 g / 10 min, the intrinsic viscosity [η] was 2.37 dl / g, and Mw was 149,00.
0, Mw / Mn was 2.10, and melting point was 110.6 ° C.

Example 5 Polymerization of Ethylene In a 1 liter autoclave which had been dried and replaced with nitrogen, 400 ml of toluene, 0.3 mmol of triisobutylaluminum, 3 micromol of biscyclopentadienyl zirconium dichloride and Example 1 (1) Got in
3 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate was added. Next, ethylene was continuously supplied to the autoclave at 70 ° C. so that the pressure in the system became 3 kg / cm ^2, and polymerization was carried out for 20 minutes. Next, 50 ml of toluene containing 0.3 mmol of trimethylaluminum was added to the system using a catalyst charging tube, and polymerization was carried out for 40 minutes while maintaining the temperature and pressure conditions. As a result, 37 g of polyethylene was obtained. The intrinsic viscosity [η] of the obtained polymer is 2.85 dl / g, Mw is 264,000, Mw / Mn is 2.72, and the melting point is 13
7.7 ° C.

Example 6 Polymerization of Ethylene In a 1 liter autoclave which had been dried and purged with nitrogen, 400 ml of toluene, 0.3 mmol of triisobutylaluminum, 1.5 micromol of biscyclopentadienyl zirconium dichloride and Example 1 ( 1.5 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate obtained in 1) was added. Next, 7
Ethylene was continuously supplied to the autoclave at 0 ° C. so that the pressure in the system became 3 kg / cm ^2, and polymerization was carried out for 20 minutes. Then, using a catalyst charging tube in the system, 0.3 mmol of trimethylaluminum, 1.5 μmol of biscyclopentadienyl zirconium dichloride and dimethylanilinium tetrakis (pentafluorophenyl) borate obtained in Example 1 (1) were used. 50 ml of toluene containing 1.5 μmol was added, and the temperature and pressure were maintained, and the polymerization was further carried out for 40 minutes. As a result, 43 g of polyethylene was obtained. The intrinsic viscosity [η] of the obtained polymer is 2.34 dl / g, Mw is 201,000, and M
w / Mn was 3.01 and the melting point was 140.1 ° C.

[0051]

As described above, according to the present invention,
It is possible to adjust the molecular weight while suppressing a decrease in activity and an increase in the molecular weight distribution, and it is possible to produce an olefin polymer having a small molecular weight distribution and a high molecular weight distribution and a large molecular weight distribution. Further, a polymer having improved and stable heat sealing performance can be produced.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a manufacturing method of the present invention.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (5)

(57) [Claims] 1. A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin using a catalyst containing the following compounds (A), (B) and (C) as main components. (A) a transition metal compound containing a tetravalent transition metal of group IVB (B) a compound which reacts with the above compound (A) to form an ionic complex (C) at least two or more kinds of organoaluminum compounds 2. The method for producing an olefin polymer according to claim 1, wherein the polymerization is carried out simultaneously using at least two or more kinds of organoaluminum compounds as the catalyst component (C). 3. The method for producing an olefin polymer according to claim 1, wherein the polymerization is carried out in a multistage polymerization step using at least two or more kinds of organoaluminum compounds as the catalyst component (C) in a stepwise manner. . 4. The method for producing an olefin polymer according to claim 3, wherein different types of catalyst components (C) are used in each stage of the multistage process. 5. The catalyst component (A) or (B) according to claim 1,
And an olefin polymerization catalyst comprising (C).