JP3493235B2 - Method for producing ethylene polymer and ethylene polymer obtained by the method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing an ethylene polymer and an ethylene polymer obtained by this method. More specifically, the present invention has a controlled molecular weight distribution, which is a feature of metallocene catalysts, has non-Newtonian properties, and is imparted with good film moldability and blow moldability, and in the molding process. The present invention relates to a method for producing an ethylene-based polymer that has low energy and cost reduction and is imparted with high-speed moldability with high efficiency, and an ethylene-based polymer obtained by this method and having the above-mentioned preferable properties. Is.

[0002]

2. Description of the Related Art In recent years, polyolefins produced by metallocene catalysts have a narrow molecular weight distribution and further have good copolymerizability with ethylene and .alpha.-olefins, so that they are expected to be used in various applications. . However, a polyolefin obtained by using the metallocene catalyst has a poor processing property due to a narrow molecular weight distribution, and as a result, has a drawback that it cannot avoid a large limitation in film molding (inflation molding) or blow molding. Therefore, it has been a problem in utilizing the metallocene-based catalysts to improve such drawbacks. As methods for improving the processing characteristics of polyolefins, methods for broadening the molecular weight distribution and methods for introducing long-chain branching have been tried so far. As a method for broadening the molecular weight distribution, for example, it is disclosed that two kinds of metallocene catalysts are used in combination (Japanese Patent Laid-Open No. 60-35006, Japanese Patent Laid-Open No. 5-350065).
No. 155932, U.S. Pat. No. 4,939,217). However, although the polyolefins obtained by these methods have a broad molecular weight distribution and improved processing characteristics, it is difficult to control low molecular weight components that adversely affect the physical properties, and physical properties are unavoidably deteriorated. Furthermore, since it is a blend in a reaction field, there is a limit to increase non-Newtonian property, swell ratio, and melt tension, which are problems in processing characteristics.

[0003]

Under the circumstances, the present invention has a controlled molecular weight distribution, which is a feature of metallocene catalysts, and has a non-Newtonian property, and has a good film formability. And blow moldability are given,
A method for producing an ethylene-based polymer with low energy and cost reduction in molding and high-speed moldability with high efficiency, and an ethylene-based polymer having the above-mentioned preferable properties obtained by this method. It was made for the purpose of providing coalescence.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that ethylene is homopolymerized or has 3 to 20 carbon atoms in the presence of a specific polymerization catalyst.
By copolymerizing ethylene with at least one selected from α-olefins, cyclic olefins, styrenes and styrene derivatives, the molecular weight distribution, which is a characteristic of metallocene catalysts, is controlled and non-Newtonian It has been found that an ethylene-based polymer having the above-mentioned preferable properties is obtained. The present invention has been completed based on such findings. That is, the present invention is
(A) General formula (I)

[0005]

[Chemical 3]

(In the formula, M is a group 3-10 group or a group of the periodic table.
Indicate the metal elements of the tantanoid series, E ¹And E²Is it
Each of which is a σ-bonding or π-bonding ligand,¹)
_p, (A²)_p, --- (Aⁿ)_pAnd (D)_sThrough
Form a cross-linked structure, and they are identical to each other
Or X may represent a σ-bonding ligand.
However, when there are plural Xs, the plural Xs are the same or different.
May be other X, E¹, E²Or even if it is crosslinked with Y
Good. Y represents a Lewis base, and when Y is plural, plural Y
Y of may be the same or different, and other Y and E¹, E
²Alternatively, it may be crosslinked with X, A¹, A², --- A
ⁿAre cross-linking groups, which are identical to each other.
May also be different. D represents a cross-linking group, and D is plural
In some cases, multiple D may be the same or different and n
Is an integer of 2 to 4, p is an integer of 1 to 4, and each p is the same.
It may be different. q is an integer of 1 to 5 [(atoms of M
Valence) -2], r is an integer of 0 to 3, s is an integer of 0 to 4
If s is 0, then (A¹)_p, (A²)_p, --- (A
ⁿ)_pAnd E²Form a direct bond. ] The transition represented by
On a metal compound, (B) another transition metal compound and (C)
From the components (A) and (B) or their derivatives,
Catalyst composed of a compound capable of forming an on-type complex
(However, the transition metal compound of the component (B) is
Group 10 to group 10 metals or lanthanide series metals
The compound containing is shown. ) In the presence of ethylene homopolymerization,
Or an α-olefin having 3 to 20 carbon atoms, a cyclic olefin
A small amount selected from among styrene, styrene and styrene derivatives.
Characterized by copolymerizing at least one kind with ethylene
The present invention provides a method for producing an ethylene-based polymer.
The present invention also relates to ethylene produced by the above method.
It is a polymer and has a resin density of 0.86 to 0.97g.
/ Ml, (b) by differential scanning calorimeter
The maximum melting peak position that can be measured is 50 to 136 ° C.
In range or practically no melting peak
Being a thing, (c) Measured at a temperature of 135 ° C in decalin
The determined intrinsic viscosity is 0.01-20 deciliters / g
And (d) gel permeation chromatograph
Polyethylene-equivalent weight average molecule
The ratio Mw / Mn between the amount (Mw) and the number average molecular weight (Mn) is
Ethylene-based heavy, characterized by being in the range of 2.0-40
It also provides coalescence. Polymerization catalyst in the present invention
Transition metal compound used as component (A) in
Is of the general formula (I)

[0007]

[Chemical 4]

A compound of multiple cross-linking type having a structure represented by
It is a thing. In the general formula (I), M is the periodic table
A metal element of Group 3 to 10 or a lanthanoid series is shown.
Examples include titanium, zirconium, hafnium,
Thorium, vanadium, chromium, manganese, nickel,
Cobalt, palladium and lanthanide series metals are listed.
Among these, olefin polymerization activity
From the point, titanium, zirconium, hafnium, chrome, bar
Nadium and lanthanide metals are preferred, especially titanium.
Ni, zirconium and hafnium are preferred. E¹Over
And E²Are σ-bonding or π-bonding ligands, respectively.
And then (A¹)_p, (A²)_p, --- (Aⁿ)_pAnd (D)
_sForm a cross-linking structure via
They may be the same or different. The E¹As a concrete example of
Is a cyclopentadienyl group, a substituted cyclopentadiene
Nyl group, indenyl group, substituted indenyl group, heterocycle
Lopentadienyl group, substituted heterocyclopentadienyl
Group, amide group (-N <), phosphide group (-P <), charcoal
Hydrogenated group [> CR-,> C <], silicon-containing group [> SiR
-,> Si <] (where R is hydrogen or 1 to 20 carbon atoms)
Is a hydrocarbon group or a heteroatom-containing group)
Named E²As a specific example of, cyclopentadiene
Group, substituted cyclopentadienyl group, indenyl group,
Substituted indenyl group, heterocyclopentadienyl group, substituted
Heterocyclopentadienyl group, amide group (-N <,-
NR-), phosphide group (-P <, -PR-), oxygen
(-O-), sulfur (-S-), selenium (-Se-), charcoal
Hydrogenated group [-C (R)₂-,> CR-,> C <], including silicon
Group [-SiR-, -Si (R)₂ -,> Si <] (ta
However, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
Or a heteroatom-containing group) and the like. Well
Further, X represents a σ-bonding ligand, and when there are plural Xs,
Multiple X's may be the same or different, other X's,
E¹, E²Alternatively, it may be crosslinked with Y. Specific examples of X
As, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
Group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, amide group having 1 to 20 carbon atoms, carbon number
1-20 silicon-containing groups, phosphides having 1-20 carbons
Group, sulfide group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Examples thereof include an acyl group. On the other hand, Y represents a Lewis base
However, when there are multiple Ys, the multiple Ys are the same or different.
May be other Y, E¹, E²Or even if it is crosslinked with X
Good. Specific examples of the Lewis base of Y include amines,
Examples of ethers, phosphines, thioethers
You can Next, A¹, A², --- AⁿIs it
Each represents a bridging group, which may be the same or different
However, at least one of the
It is preferred that it is composed only of
Yes. Here, at least one is made of carbon.
Comprising only a bridge means the formula

[0009]

[Chemical 5]

(R¹And R²Are the hydrogen atom and
Rogen atom, C1-C20 hydrocarbon group, C1-C1
20 halogen-containing hydrocarbon groups, silicon-containing groups or hetero
Atom-containing groups, which may be the same or different
It may be bonded to each other to form a ring structure,
p shows the integer of 1-4. )
means. As a specific example of such a cross-linking group, for example,
For example, methylene, ethylene, ethylidene, isopropylide
, Cyclohexylidene, 1,2-cyclohexylene,
Vinylidene (CH₂= C =) and the like. Also,
A¹~ AⁿOther specific structure of R'is₂S
i, R '₂Ge, R '₂Sn, R'Al, R'P, R'P
(= O), R'N, oxygen (-O-), sulfur (-S-),
Selenium (-Se) [wherein R'is hydrogen atom, halogen
Atom, hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Halogen-containing hydrocarbon group, silicon-containing group or hetero atom-containing group
Group, and when R'is two, they are the same or different
Can be attached to each other to form a ring structure
You may stay. ] Etc. are mentioned. Of such bridging groups
Specific examples include dimethylsilylene and tetramethyldisi
Rylene, dimethylgermylene, dimethylstannylene,
Chilboriden (CH₃-B <), methylaluminidene
(CH₃-Al <), phenylphosphylidene (Ph-
P <), phenylphosphoridene (Ph-P (= O)
<), Methylimide, oxygen (-O-), sulfur (-S-), se
Ren (-Se-) and the like. Furthermore, A¹ ~ Aⁿage
And vinylene (-CH = CH-), o-xylylene (f
Phenyl-1,2-dimethylene); 1,2-phenylene
I can name them. D represents a cross-linking group, and D is plural
In some cases, multiple D's may be the same or different. The
Specific examples of D include R ″ C, R ″ Si, R ″ Ge, R ″
Sn, B, Al, P, P (= O), N (where R '' is
Hydrogen atom, halogen atom, hydrocarbon having 1 to 20 carbon atoms
Group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group
It is a group or a group containing a hetero atom. ) Etc.
You can n is an integer of 2 to 4, p is an integer of 1 to 4,
p may be the same or different, and q is 1 to 5
It represents an integer [(valence of M) -2], and r is an integer of 0 to 3.
Number, s is an integer from 0 to 4, and when s is 0, (A¹)_p，
(A²)_p, --- (Aⁿ)_pAnd E²Form a direct bond
It In the compounds represented by the general formula (I), s is 0
In the case of, that is, the general formula (II) having no crosslinking group of D

[0011]

[Chemical 6]

(Where M, E ¹ , E ² , X, Y, A ¹ ,
A ² , --- A ⁿ , n, p, q and r are the same as above. ) And a transition metal compound in which at least one of A ¹ , A ² , and --A ⁿ is composed only of a bridge by carbon is preferable. Specific examples of the transition metal compound represented by the general formula (I) include (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) zirconium dichloride, (1 ，
1'-dimethylsilylene) (2,2'-dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-
Isopropylidene) -bis (cyclopentadienyl) zirconium dimethyl, (1,1'-dimethylsilylene)
(2,2'-isopropylidene) -bis (cyclopentadienyl) zirconium dibenzyl, (1,1'-dimethylsilylene) (2,2'-isopropylidene) -bis (cyclopentadienyl) zirconium bis ( (Trimethylsilyl), (1,1'-dimethylsilylene) (2,
2'-isopropylidene) -bis (cyclopentadienyl) zirconium bis (trimethylsilylmethyl),
(1,1′-Dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) zirconium dimethoxide, (1,1′-dimethylsilylene)
(2,2′-isopropylidene) -bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), (1,1′-dimethylsilylene) (2,2
2'-methylene) -bis (cyclopentadienyl) zirconium dichloride, (1,1'-ethylene) (2,
2'-methylene) -bis (cyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-ethylene) -bis (indenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-
Dimethylsilylene) -bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,
2'-Cyclohexylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1'-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,1'-isopropylidene) (2,2'-dimethylsilylene) -bis (indenyl) zirconium dichloride, (1,1'-dimethyl) Silylene) (2,2'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1'-Dimethylsilylene) (2,2'-isopropylidene) -bis (indenyl) zirconium dimethyl, (1,1 ') -Dimethylsilylene) (2,2'-isopropylidene) -bis (indenyl) zirconium dibenzyl, (1,1 '
-Dimethylsilylene) (2,2'-isopropylidene)
-Bis (indenyl) zirconium bis (trimethylsilyl), (1,1'-dimethylsilylene) (2,2'-
Isopropylidene) -bis (indenyl) zirconium bis (trimethylsilylmethyl), (1,1'-dimethylsilylene) (2,2'-isopropylidene) -bis (indenyl) zirconium dimethoxide, (1,1 '
-Dimethylsilylene) (2,2'-isopropylidene)
-Bis (indenyl) zirconium bis (trifluoromethanesulfonate), (1,1'-dimethylsilylene) (2,2'-isopropylidene) -bis (4,5,5
6,7-Tetrahydroindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) (2,2′- Isopropylidene) -bis (indenyl) zirconium dichloride,
(1,1'-isopropylidene) (2,2'-ethylene) -bis (indenyl) zirconium dichloride,
(1,1′-isopropylidene) (2,2′-isopropylidene) -bis (cyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2
2'-isopropylidene)-(3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene) Reden)-(4
-Methylcyclopentadienyl) (4'-methylcyclopentadienyl) zirconium dichloride, (1,1 '
-Dimethylsilylene) (2,2'-isopropylidene)
-(3,4,5-Trimethylcyclopentadienyl)
(3 ', 4', 5'-Trimethylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene)-(4-n-
Butylcyclopentadienyl) (4′-n-butylcyclopentadienyl) zirconium dichloride, (1,
1'-dimethylsilylene) (2,2'-isopropylidene) (4-tert-butylcyclopentadienyl)
(4'-tert-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1'-isopropylidene)-(3-methylindenyl) (3'-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene)-(3- Methylindenyl) (3'-
Methylindenyl) zirconium dichloride, (1,
1'-isopropylidene) (2,2'-dimethylsilylene)-(3-methylindenyl) (indenyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-isopropylidene)-(4,7-dimethylindenyl) (indenyl) zirconium dichloride,
(1,1'-Dimethylsilylene) (2,2'-isopropylidene)-(4,5-benzoindenyl) (indenyl) zirconium dichloride, (1,1'-Dimethylsilylene) (2,2'-isopropylidene) Reden)-(4,7-
Dimethylindenyl) (4 ', 7'-dimethylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene)-(4,5-
Benzoindenyl) (4,5-benzoindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2'-isopropylidene)-(3-methylindenyl) (3'-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene)-(3- Ethylindenyl) (3'-
Ethylindenyl) zirconium dichloride, (1,
1'-Dimethylsilylene) (2,2'-isopropylidene)-(3-n-butylindenyl) (3'-n-butylindenyl) zirconium dichloride, (1,1'-
Dimethylsilylene) (2,2'-isopropylidene)-
(3-tert-butylindenyl) (3'-tert
-Butylindenyl) zirconium dichloride, (1,
1'-dimethylsilylene) (2,2'-isopropylidene)-(3-trimethylsilylindenyl) (3'-trimethylsilylindenyl) zirconium dichloride,
(1,1′-Dimethylsilylene) (2,2′-isopropylidene)-(3-benzylindenyl) (3′-benzylindenyl) zirconium dichloride, (1,1 ′
-Dimethylsilylene) (2,2'-ethylene)-(indenyl) (cyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene)-(indenyl) (cyclopenta Dienyl) zirconium dichloride, (3,3′-isopropylidene) (4,4′-isopropylidene)-(1-phosphacyclopentadienyl) (1′-phosphacyclopentadienyl) zirconium dichloride, ( 3,1 '
-Isopropylidene) (4,2'-isopropylidene)
Examples thereof include-(1-phosphacyclopentadienyl) (4'-cyclopentadienyl) zirconium dichloride, and compounds in which zirconium in these compounds is replaced with titanium or hafnium. Of course, it is not limited to these. Further, it may be a compound similar to a metal element of another group or lanthanoid series.

In the polymerization catalyst of the present invention, (B)
The transition metal compound used as a component is not particularly limited and various compounds can be mentioned, but the general formula CpM ¹ R ³ _a R ⁴ _b R ⁵ _c (III) Cp ₂ M ¹ R ³ _a R ⁴ _{b ··· (IV) (Cp-} A e -Cp) M 1 R 3 a R 4 b ··· (V) or the general formula _{^{M 1 R 3 a R 4 b}} R 5 c R 6 d ··· ( The compound represented by VI) or a derivative thereof is preferable.

In the above general formulas (III) to (VI), M ¹
Represents a transition metal such as titanium, zirconium, hafnium, vanadium, chromium, or a lanthanoid series, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group,
A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a σ-bonding ligand, a chelating ligand, a ligand such as a Lewis base, and as the σ-bonding ligand, Specifically, hydrogen atom, oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, halogen atom, carbon number 1 to
Examples thereof include an alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, an allyl group, a substituted allyl group, and a substituent containing a silicon atom. An alkoxy group, an amino group or an acyloxy group is preferable. Examples of chelating ligands include acetylacetonate groups and substituted acetylacetonate groups. A indicates crosslinking by covalent bond. a,
b, c and d are each independently an integer of 0 to 4 and e is 0 to
An integer of 6 is shown. R ³ , R ⁴ , R ⁵ and R ⁶ are the two
The above 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 (IV) and (V), the two Cp may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above formulas (III) to (V) include methylcyclopentadienyl group, ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclohexyl group. Pentadienyl group; tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. In addition, (III) ~
Specific examples of R ^{3 to} R ^{6 in} the formula (VI) include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom,
Iodine atom, C1-C20 alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-
Aryl group having 6 to 20 carbon atoms such as butyl group, octyl group and 2-ethylhexyl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group and benzyl group. As a substituent containing a silicon atom such as a heptadecylcarbonyloxy group, a trimethylsilyl group as a substituent containing a silicon atom, a (trimethylsilyl) methyl group, etc. Group, isobutoxy group, s
ec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, alkoxy group such as octoxy group, cyclohexoxy group, and aryloxy group such as phenoxy group; Group, phenylthio group, further methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, isopropanesulfonyl group, n-
Butanesulfonyl group, sec-butanesulfonyl group, t
A dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a diisopropylamino group as a substituent containing a nitrogen atom, such as an alkylsulfonyl group such as a butanesulfonyl group and an isobutanesulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group. , Di (n-butyl) amino group, diisobutylamino group, di (sec-butyl) amino group, di (t-butyl) amino group, dipentylamino group, dihexylamino group, dioctylamino group, diphenylamino group, dibenzyl Amino group, methylethylamino group, (t-butyl) trimethylsilylamino group, methyltrimethylsilylamino group and the like, as a substituent containing a phosphorus atom, a dimethylphosphido group, a diethylphosphido group, a di (n-propyl) phosphido group,
Diisopropylphosphido group, di (n-butyl) phosphido group, diisobutylphosphido group, di (sec
-Butyl) phosphido group, di (t-butyl) phosphido group, dipentylphosphido group, dihexylphosphido group, dioctylphosphido group, diphenylphosphido group, dibenzylphosphido group, methylethylphosphido group, (t- (Butyl) trimethylsilyl phosphido group, methyl trimethylsilyl phosphido group, etc. as Lewis bases such as ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, acetonitrile; nitriles such as benzonitrile , Trimethylamine; triethylamine; tributylamine; N, N-dimethylaniline;
Pyridine; 2,2'-bipyridine; amines such as phenanthroline; triethylphosphine; phosphines such as triphenylphosphine; ethylene; butadiene;
1-Pentene; Isoprene; Pentadiene; Chain unsaturated hydrocarbons such as 1-hexene and derivatives thereof, benzene; Toluene; Xylene; Cycloheptatriene; Cyclooctadiene; Cyclooctatriene; Cyclooctatetraene and derivatives thereof And cyclic unsaturated hydrocarbons. In addition, A in the above formula (V)
Examples of the cross-linking by covalent bond include methylene cross-link, dimethyl methylene cross-link, ethylene cross-link, 1,1′-
Examples include cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of the transition metal compound represented by the general formula (III) include cyclopentadienyl titanium trimethyl; cyclopentadienyl titanium triethyl; cyclopentadienyl titanium tri (n-propyl); cyclopentadiene. Cyclopentadienyl titanium tri (n-butyl); cyclopentadienyl titanium triisobutyl; cyclopentadienyl titanium tri (sec-butyl); cyclopentadienyl titanium tri (t-butyl); methyl 1,2-dimethylcyclopentadienyl titanium trimethyl; 1,2,4-trimethylcyclopentadienyl titanium trimethyl; 1,2,3,4-tetramethylcyclopentadienyl titanium trimethyl; Pentamethylcyclopen Pentamethylcyclopentadienyl titanium triethyl; pentamethylcyclopentadienyl titanium tri (n-propyl); pentamethylcyclopentadienyl titanium triisopropyl; pentamethylcyclopentadienyl titanium tri (n-butyl) ); Pentamethylcyclopentadienyl titanium triisobutyl; pentamethylcyclopentadienyl titanium tri (sec-butyl); pentamethylcyclopentadienyl titanium tri (t-butyl); pentamethylcyclopentadienyl titanium tribenzyl; Cyclopentadienyl titanium trimethoxide; Cyclopentadienyl titanium triethoxide; Cyclopentadienyl titanium tri (n-propoxide); Cyclopentadienyl titanium triisopropoxide; Pentadienyl titanium triphenoxide; Methylcyclopentadienyl titanium trimethoxide; (n-Butyl) cyclopentadienyl titanium trimethoxide; Dimethylcyclopentadienyl titanium trimethoxide; Dimethylcyclopentadienyl titanium triethoxide Dimethylcyclopentadienyl titanium tri (n-propoxide); dimethylcyclopentadienyl titanium triisopropoxide; dimethylcyclopentadienyl titanium triphenoxide; di (t-butyl) cyclopentadienyl titanium trimethoxide; Di (t-butyl) cyclopentadienyl titanium triethoxide; di (t-butyl) cyclopentadienyl titanium tri (n-propoxide); di (t-butyl) cyclopentadienyl titanium triisopropoxide; The (t Butyl) cyclopentadienyl titanium tri phenoxide; bis (trimethylsilyl) cyclopentadienyl titanium trimethoxide; bis (trimethylsilyl) cyclopentadienyl titanium triethoxide; bis (trimethylsilyl) cyclopentadienyl titanium tri (n-
Propoxide); bis (trimethylsilyl) cyclopentadienyl titanium triisopropoxide; bis (trimethylsilyl) cyclopentadienyl titanium triphenoxide; trimethylcyclopentadienyl titanium trimethoxide; trimethylcyclopentadienyl titanium triethoxide; Trimethylcyclopentadienyl titanium tri (n-propoxide); trimethylcyclopentadienyl titanium triisopropoxide; trimethylcyclopentadienyl titanium triphenoxide; triethylcyclopentadienyl titanium trimethoxide; [bis (trimethylsilyl), Methyl] cyclopentadienyl titanium trimethoxide; [di (t-butyl, methyl)] cyclopentadienyl titanium triethoxide; tetramethylcyclopentadienyl Tantrimethoxide; tetramethylcyclopentadienyl titanium triethoxide; tetramethylcyclopentadienyl titanium tri (n-propoxide); tetramethylcyclopentadienyl titanium triisopropoxide; tetramethylcyclopentadienyl titanium Tri (n-butoxide); Tetramethylcyclopentadienyl titanium triisobutoxide; Tetramethyl cyclopentadienyl titanium tri (sec-butoxide); Tetramethyl cyclopentadienyl titanium tri (t-butoxide); Tetramethyl cyclopenta Dienyl titanium triphenoxide; [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium triethoxide; [ Tramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4-methoxyphenyl] cyclopenta Dienyl titanium triphenoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium Tri (n-propoxide); [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, benzyl] Cyclopentadienyl titanium trimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, benzyl]
Cyclopentadienyl titanium triisopropoxide;
[Tetramethyl, benzyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 2-
Methoxyphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, ethyl] cyclopentadioxide Phenyl titanium tri (n-propoxide); [tetramethyl, ethyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, ethyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, n-butyl] cyclopenta Dienyl titanium trimethoxide; [tetramethyl, n
-Butyl] cyclopentadienyl titanium triethoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium tri (n-propoxide); [tetramethyl,
[n-Butyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, phenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, phenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, trimethylsilyl] Cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide;
Pentamethylcyclopentadienyl titanium tri (n-propoxide); pentamethylcyclopentadienyl titanium triisopropoxide; pentamethylcyclopentadienyl titanium tri (n-butoxide); pentamethylcyclopentadienyl titanium triiso Butoxide; pentamethylcyclopentadienyl titanium tri (sec-butoxide); pentamethylcyclopentadienyl titanium tri (t-butoxide); pentamethylcyclopentadienyl titanium tri (cyclohexoxide); pentamethylcyclopentadienyl Titanium triphenoxide; cyclopentadienyl titanium tribenzyl; indenyl titanium trimethoxide; indenyl titanium triethoxide; indenyl titanium trimethyl; indenyl titanium tribenzyl; cyclopen Dienyl titanium tri (methanesulfonyl); trimethyl cyclopentadienyl titanium (tri benzenesulfonyl); tetramethylcyclopentadienyl titanium tri (ethanesulfonyl); pentamethylcyclopentadienyltitanium tri (methanesulfonyl);
Cyclopentadienyl titanium tris (dimethylamine); trimethylcyclopentadienyl titanium tris (dimethylamine); pentamethylcyclopentadienyl titanium tris (dibenzylamine); pentamethylcyclopentadienyl titanium tris (dimethylamine);
Pentamethylcyclopentadienyl titanium tris (diethylamine); cyclopentadienyl titanium tri (nitro); pentamethylcyclopentadienyl titanium tri (nitro), etc., and compounds in which titanium in these compounds is replaced with zirconium or hafnium Can be mentioned.

Further, cyclopentadienyl titanium dimethyl monochloride; cyclopentadienyl titanium monoethyl dichloride; cyclopentadienyl titanium di (n
-Propyl) monochloride; cyclopentadienyl titanium diisopropyl monochloride; cyclopentadienyl titanium di (n-butyl) monochloride; cyclopentadienyl titanium diisobutyl monochloride; cyclopentadienyl titanium di (sec-butyl) mono Chloride; cyclopentadienyl titanium di (t-butyl) monochloride; 1,2-dimethylcyclopentadienyl titanium dimethyl monochloride; 1,2,4-trimethylcyclopentadienyl titanium dimethyl monochloride; Three
4-Tetramethylcyclopentadienyl titanium dimethyl monochloride; pentamethyl cyclopentadienyl titanium dimethyl monochloride; cyclopentadienyl titanium monochlorodimethoxide; cyclopentadienyl titanium dichloromonomethoxide; cyclopentadienyl titanium dichloromonochloride Ethoxide; Cyclopentadienyl titanium monochlorodioxide (n-propoxide); Cyclopentadienyl titanium monochlorodiisopropoxide; Cyclopentadienyl titanium monochlorodiphenoxide; Dimethylcyclopentadienyl titanium monochlorodimethoxide;
Dimethylcyclopentadienyl titanium monochlorodiethoxide; Dimethylcyclopentadienyl titanium monochlorodioxide (n-propoxide); Dimethylcyclopentadienyl titanium monochlorodiisopropoxide; Dimethylcyclopentadienyl titanium monochlorodiphenoxide;
Di (t-butyl) cyclopentadienyl titanium monochlorodimethoxide; Bis (trimethylsilyl) cyclopentadienyl titanium monochlorodimethoxide; Trimethylcyclopentadienyl titanium monochlorodimethoxide;
Trimethylcyclopentadienyl titanium monochlorodiphenoxide; triethylcyclopentadienyl titanium monochlorodimethoxide; [bis (trimethylsilyl),
Methyl] cyclopentadienyl titanium monochlorodimethoxide; tetramethylcyclopentadienyl titanium monochlorodimethoxide; tetramethylcyclopentadienyl titanium dichloromonomethoxide; tetramethylcyclopentadienyl titanium monochlorodimethoxide (n-butoxide); tetra Methylcyclopentadienyl titanium monochloroisobutoxide; Tetramethylcyclopentadienyl titanium monochlorodi (sec-butoxide); Tetramethylcyclopentadienyl titanium monochlorodi (t
-Butoxide); [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium monochlorodimethoxide; [tetramethyl, 4-methylphenyl] cyclopentadienyl titanium monochlorodimethoxide; [tetramethyl, benzyl] cyclopentadienyl Titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodiphenoxide; [Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochloro Dimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl, n-
Butyl] cyclopentadienyl titanium monochlorodiethoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium monochlorodi (n-propoxide); [tetramethyl, n-butyl] cyclopentadienyl titanium monochlorodiiso Propoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium monochlorodimethoxide; pentamethylcyclopentadienyl titanium monochlorodimethoxide; pentamethylcyclopentadienyl Pentamethylcyclopentadienyl titanium monochlorodiethoxide; Pentamethylcyclopentadienyl titanium monochlorodioxide (cyclohexoxide); Pentadienyl titanium monochlorodiphenoxide; Indenyl titanium monochlorodimethoxide; Cyclopentadienyl titanium monochlorodiene (methanesulfonyl); Pentamethylcyclopentadienyl titanium monochlorobis (diethylamine); Pentamethylcyclopentadienyl titanium monochlorobis [ Di (n-butyl) amine]; pentamethylcyclopentadienyl titanium dichloro (dimethylamine); pentamethylcyclopentadienyl titanium dimethoxy (dimethylamine); pentamethylcyclopentadienyl titanium dichloro (diphenylamine); pentamethylcyclo Pentadienyl titanium dichloro (methylethylamine); Pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilylamine); Cyclopentadienyl titanium dimethoxy (diphenylamine);
Pentamethylcyclopentadienyl titanium monochlorobis (diethylphosphide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) phosphide]; pentamethylcyclopentadienyl titanium dichloro (dimethylphosphide); pentamethyl Cyclopentadienyl titanium dimethoxy (dimethyl phosphide); pentamethyl cyclopentadienyl titanium dichloro (diphenyl phosphide); pentamethyl cyclopentadienyl titanium dichloro (methyl ethyl phosphide); pentamethyl cyclopentadienyl titanium dichloro ( t-butyltrimethylsilyl phosphide);
Pentamethylcyclopentadienyl titanium dimethoxy (diphenylphosphide) and the like, as well as compounds in which titanium in these compounds is substituted with zirconium, hafnium, chromium, etc., and metal elements of Groups 8 to 10 of the periodic table and lanthanoid series Can be mentioned.

Examples of the compound represented by the general formula (IV) include bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis ( Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) Dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium,
Bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) methoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium chloride, bis (cyclopentadienyl) butoxyzirconium chloride, bis (cyclopentadienyl) ) 2-Ethylhexoxy zirconium chloride, bis (cyclopentadienyl) methyl zirconium ethoxide, bis (cyclopentadienyl) methyl zirconium butoxide, bis (cyclopentadienyl) ethyl zirconium ethoxide, bis (cyclopentadienyl) ) Phenylzirconium chloride, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) benzylzirconium ethoxide, bis (methylcyclopep tide) Tadienyl) ethoxyzirconium chloride, bis (indenyl) ethoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium, bis (cyclopentadienyl) butoxyzirconium, bis (cyclopentadienyl) 2-ethylhexoxyzirconium, bis ( Cyclopentadienyl)
Phenoxyzirconium chloride, bis (cyclopentadienyl) cyclohexoxyzirconium chloride, bis (cyclopentadienyl) phenylmethoxyzirconium chloride, bis (cyclopentadienyl) methylzirconium phenylmethoxide, etc. Alternatively, a compound in which hafnium is substituted is included.

Examples of the compound represented by the general formula (V) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl).
Dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) Dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9 -Fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexalidene (9-fluorenyl ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, etc. Alternatively, a compound can be given by substituting with hafnium.

Further, examples of the compound represented by the general formula (VI) include tetramethylzirconium, tetrabenzylzirconium, tetrachlorozirconium, tetrabromozirconium, zirconium bis (acetylacetonate), tetraethoxyzirconium and tetramethoxy. Examples thereof include zirconium, butoxytrichlorozirconium, tetrabutoxyzirconium, butoxydichlorozirconium, and compounds in which zirconium is replaced with titanium or hafnium. Specific examples of vanadium compounds include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadiene. Examples thereof include dienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium dichloride, dicyclopentadienylmethyl vanadium and the like.

Next, specific examples of the chromium compound include tetramethyl chromium, bis (cyclopentadienyl) chromium, and hydride tricarbonyl (cyclopentadienyl).
Chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyl tris (triphenylphosphonate) chromium, tris (allyl)
Examples thereof include chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like. Further, as the component (B), in the above general formula (V), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). It is possible to use a Group 4 transition metal compound having a ligand of a multicoordinating compound bonded to each other through an element selected from Group 14 of the periodic table. As such a compound, for example, a compound represented by the general formula (VII)

[0022]

[Chemical 7]

The compounds represented by
be able to. Y in the general formula (VII)¹Is carbon, Kei
Element, germanium or tin atom, R⁷ _f-C_FiveH_4-fOver
And R⁷ _u-C_FiveH_4-uAre each substituted cyclopentadi
The enyl group, f and u represent an integer of 1 to 4. here,
R⁷Are hydrogen atoms, silyl groups or hydrocarbon groups, and
May be the same or different. Also, at least
Also, one cyclopentadienyl group contains Y¹Combined with
R on at least one carbon next to the existing carbon⁷Exists
It R⁸Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or
C6-C20 aryl group, alkylaryl group
Represents an arylalkyl group. M²Is titanium, zirco
X represents a nitrogen or hafnium atom, and X¹Is a hydrogen atom,
Rogen atom, C1-C20 alkyl group, C6-C
20 aryl groups, alkylaryl groups or aryl
Represents a rualkyl group. X¹Are the same but different
R may⁸Even though they are the same as each other,
You may stay.

Examples of the substituted cyclopentadienyl group in the above general formula (VII) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, Examples of the 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ⁸ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group.

Specific examples of the compound represented by the above general formula (VII) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2,3,5-trimethyl). Cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride, isopropylidenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, etc. . Furthermore, the general formula (VIII)

[0026]

[Chemical 8]

The compounds represented by are also included. The general formula (V
In the compound of III), Cp is a cyclic unsaturated such as cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group. A hydrocarbon group or a chain unsaturated hydrocarbon group is shown. M ³ represents a titanium, zirconium or hafnium atom, X ² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, or 1 carbon atom. ~ 20 alkoxy groups are shown. Z is Si
R ⁹ ₂ , CR ⁹ ₂ , SiR ⁹ ₂ SiR ⁹ ₂ , CR ⁹ ₂ CR ⁹ ₂ , CR
_{^{9 2 CR 9 2 CR 9 2}} , CR 9 = CR 9, CR 9 2 shows a SiR ⁹ ₂ or GeR ^{9 _2,} Y ₂ is ^{-N (R 10) -, -} O -, - S
- or -P (R ¹⁰⁾ - shows the. R ⁹ is a hydrogen atom or a group selected from alkyl, aryl, silyl, alkyl halide, aryl halide groups having up to 20 non-hydrogen atoms and combinations thereof, and R ¹⁰ is a group having 1 carbon atom.
It may be an alkyl group having 10 to 10 or an aryl group having 6 to 10 carbon atoms, or may form a fused ring system of one or more R ⁹ and up to 30 non-hydrogen atoms. w represents 1 or 2.

Specific examples of the compound represented by the above general formula (VIII) include (tertiary butylamide) (tetramethyl-
η ⁵ -Cyclopentadienyl) -1,2-ethanediylzirconium dichloride; (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediyl titanium dichloride; (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediyl zirconium dichloride; (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride; (ethylamido) (tetramethyl- [eta] ⁵ -cyclopentadienyl)-
Methylene titanium dichloride; (tertiary butylamide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride; (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl; (benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride; (phenylphosphide) dimethyl (tetramethyl- [eta] ⁵ -cyclopentadienyl) silane zirconium dibenzyl and the like.

Further, the general formula (IX)

[0030]

[Chemical 9]

The compounds represented by are also included. In the general formula (IX), R ¹¹ represents an alkyl group having 1 to 20 carbon atoms or an acyl group, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group. Shown, each R ¹¹ may be the same or different. M ⁴ represents a metal element of Group 3 or ⁴ of the periodic table or a lanthanoid series, and z represents an integer of 2 to 20.

Specific examples of the compound represented by the general formula (IX) include BuO [Zr (OBu) ₂ O] ₄ -Bu,
Examples thereof include EtO [Zr (OEt) ₂ O] ₄ -Et and the like, and compounds in which zirconium is replaced with titanium or hafnium. Note that Bu represents a butyl group and Et represents an ethyl group. Preferable examples of these transition metal compounds include transition metal compounds having an alkoxy group, an amino group or an acyloxy group as a σ-bonding ligand, particularly the above-mentioned transition metal compounds containing a cyclopentadienyl type ligand. It can be illustrated. In the polymerization catalyst of the present invention, it is preferable to use, as the component (A) and / or the component (B), a transition metal compound that forms a terminal vinyl group in homopolymerization or copolymerization of ethylene.

In the polymerization catalyst of the present invention, the transition metal compounds of the above components (A) and (B) may be used alone or in combination of two or more. On the other hand, in the polymerization catalyst, as the compound used as the component (C), a compound capable of forming an ionic complex from the transition metal compound of the components (A) and (B) or a derivative thereof is (C-1). The ionic compound which reacts with the transition metal compound of said (A) and (B) and forms an ionic complex, and (C-2) aluminoxane can be illustrated. Examples of the compound of the component (C-1) include the above (A)
And any ionic compound capable of reacting with the transition metal compound of the component (B) to form an ionic complex, but a compound comprising a cation and an anion in which a plurality of groups are bound to an element Particularly, a coordination complex compound composed of a cation and an anion in which a plurality of groups are bound to an element can be preferably used. Examples of the compound such cations and a plurality of groups consisting of anions bonded to an element of the general formula ([L ¹ -R ^{12] k +)} _i ^{([M 5 Z 1 Z 2 ·· Z} n ] ^{(hg) -} ) _J ·· (X) or ([L ² ] ^{k +} ) _i ([M ⁶ Z ¹ Z ² ·· Z ⁿ ] ^(hg)- ) _j ·· (XI) (where L ² is M ⁷ , R ¹³ R ¹⁴ M ⁸ , R ¹⁵ ₃ C or R ¹⁶
M ⁸ ) [In the formula, L ¹ is a Lewis base, M ⁵ and M ⁶ are 5 group, 6 group, 7 group, 8 group, 10 group, 11 group, 1 of the periodic table, respectively.
An element selected from Group 2, 13, 14 and 15 groups, preferably an element selected from Group 13, 14 and 15 groups,
M ⁷ and M ⁸ are the groups 3, 4 and 5 of the periodic table, respectively.
Tribe, 6 family, 7 family, 8-10 family, 1 family, 11 family, 2 family, 1
Elements selected from Group 2 and Group 17, Z ^{1 to} Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. A group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, 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 ¹² 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, and R ¹³ and R ¹⁴
Are a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁵
Represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁶ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. g is an valence of M ⁵ and M ⁶ and is an integer of 1 to 7, h is an integer of 2 to 8 and k is [L ¹ -R ¹² ], [L ² ].
Is an integer of 1 to 7 in the valence of i, i is an integer of 1 or more, j =
(I × k) / (h−g). ] It is a compound represented by these.

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

As specific examples of M ⁵ and M ⁶ ,
B, Al, Si, P, As, Sb, etc., preferably B or P, M ⁷ are exemplified by Li, Na, Ag, C.
Specific examples of M ⁸ , such as u, Br, and I, include Mn and F.
e, Co, Ni, Zn, etc. may be mentioned. Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group as a dialkylamino group; a diethylamino group, a methoxy group, an ethoxy group, an n-butoxy group, and a carbon number of 6 to 20 as an alkoxy group having 1 to 20 carbon atoms. Phenoxy group as an aryloxy group; 2,6-dimethylphenoxy group; naphthyloxy group, methyl group as an alkyl group having 1 to 20 carbon atoms;
Ethyl group; n-propyl group; isopropyl group; n-butyl group; n-octyl group; 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms; phenyl group as an alkylaryl group or arylalkyl group; p-tolyl group Benzyl group; 4-t-butylphenyl group; 2,6-dimethylphenyl group; 3,5-dimethylphenyl group; 2,4-
Dimethylphenyl group; 2,3-dimethylphenyl group; p-fluorophenyl group as halogen-substituted hydrocarbon group having 1 to 20 carbon atoms; 3,5-difluorophenyl group; pentachlorophenyl group; 3,4,5-trifluoro group Phenyl group; pentafluorophenyl group; 3,5-di (trifluoromethyl) phenyl group, F, C as halogen atom
1, Br, I, pentamethylantimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group,
Examples thereof include diphenylarsine group, dicyclohexylantimony group, and diphenylboron group. Specific examples of R ¹² and R ¹⁵ include the same as those mentioned above. Specific examples of the substituted cyclopentadienyl group for R ¹³ and R ¹⁴ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. To be Here, the alkyl group usually has 1 to 6 carbon atoms,
The number of substituted alkyl groups is an integer of 1-5.

Among the compounds of the above general formulas (X) and (XI), those in which M ⁵ and M ⁶ are boron are preferable. Among the compounds of the general formulas (X) and (XI), the following compounds can be used particularly preferably. For example, examples of the compound of the general formula (X) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyltri (n-butyl tetraphenylborate). Ammonium, benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzyl tetraphenylborate Rumethylsulfonium, triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrabutylammonium tetrakis (pentafluorophenyl) borate , Tetrakis (pentafluorophenyl) borate tetraethylammonium, tetrakis (pentafluorophenyl) borate [methyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) ) Methyldiphenylammonium borate, Methyltriphenylammonium tetrakis (pentafluorophenyl) borate, Tetrakis (pentafluorophenyl) borate dimethyl diphenyl ammonium tetrakis (pentafluorophenyl) borate anilinium tetrakis (pentafluorophenyl) borate-methyl anilinium,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl tetrakis (pentafluorophenylmethyl) borate (p- Bromoanilinium), pyridinium tetrakis (pentafluorophenyl) borate, 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-) Benzylpyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium, tetrakis (pentafluorophenyl) borate benzyldimethylsulfonium, tetrakis (pentafluorophenyl) borate tetrafelphosphonium, tetrakis (3,5-ditrifluoromethylphenyl) borate dimethylani Lithium, tris (pentafluorophenyl)
Dimethylanilinium (p-trifluoromethyltetrafluorophenyl) borate, triethylammonium tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) ) Pyridinium borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (N-methylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (O-cyano- N-methylpyridinium), tris (pentafluorophenyl)
(P-Trifluoromethyltetrafluorophenyl) borate (p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate triphenylphosphonium, tris (pentafluorophenyl) ( 2, 3, 5,
Dimethylanilinium 6-tetrafluoropyridinyl) borate, tris (pentafluorophenyl) (2,3,3
5,6-Tetrafluoropyridinyl) borate triethylammonium, tris (pentafluorophenyl) (2,
3,5,6-Tetrafluoropyridinyl) pyridinium borate, tris (pentafluorophenyl) (2,3,3
5,6-Tetrafluoropyridinyl) boric acid (N-methylpyridinium), tris (pentafluorophenyl)
(2,3,5,6-tetrafluoropyridinyl) boric acid (O-cyano-N-methylpyridinium), tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) boric acid ( p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (2,
3,5,6-Tetrafluoropyridinyl) borate triphenylphosphonium, tris (pentafluorophenyl)
Dimethylanilinium (phenyl) borate, Tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] dimethylanilinium borate, Tris (pentafluorophenyl) (4-trifluoromethylphenyl) dimethylanilinium borate , Dimethylanilinium triphenyl (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, and the like.

On the other hand, as the compound of the general formula (XI), tetraphenyl borate ferrocenium tetraphenyl borate silver, tetraphenyl borate trityl, tetraphenyl borate (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) ferrocenium borate, Tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), Tetrakis (pentafluorophenyl) decamethylferrocenium borate, Tetrakis (pentafluorophenyl) borate acetylferrocenium, Tetrakis (pentafluorophenyl) Formylferrocenium borate, Tetrakis (pentafluorophenyl) borate cyanoferrocenium, Tetrakis (pentafluorophenyl) silver borate, Tetrakis (pentafluorophenyl) borate tritiate , Lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetrakis ( Pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate and the like can be mentioned. In addition, as compounds other than the general formulas (X) and (XI), for example, tris (petafluorophenyl) boron, tris [3,5-di (trifluoromethyl) phenyl] boron, triphenylboron, etc. are also used. can do. The ionic compound which is the component (C-1) and which reacts with the transition metal compound of the components (A) and (B) to form an ionic complex may be used alone or in combination of two or more. You may use. Further, the component composed of the transition metal compound of the components (A) and (B) and the ionic compound capable of forming the ionic complex of the component (C-1) may be a polycation complex. On the other hand, the aluminoxane as the component (C-2) is represented by the general formula (XII)

[0038]

[Chemical 10]

[Wherein R ¹⁷ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
A hydrocarbon group such as an arylalkyl group, v represents the degree of polymerization, and is generally an integer of 3 to 50, preferably 7 to 40. ] The chain aluminoxane represented by the general formula (XI
II)

[0040]

[Chemical 11]

[In the formula, R ¹⁷ and v are the same as defined above. ] The cyclic aluminoxane represented by these can be mentioned. Among the compounds of the general formulas (XII) and (XIII), aluminoxane having a degree of polymerization of 7 or more is preferable. When the aluminoxane having a degree of polymerization of 7 or more or a mixture thereof is used, high activity can be obtained. Further, a modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the general formulas (XII) and (XIII) with a compound having active hydrogen such as water can also be preferably used. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, an organoaluminum compound is dissolved in an organic solvent, a method of contacting it with water, a method of initially adding an organoaluminum compound at the time of polymerization, and a method of subsequently adding water, water of crystallization contained in a metal salt, A method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, reacting a tetraalkyldialuminoxane with a trialkylaluminum,
Furthermore, there is a method of reacting water. These aluminoxanes may be used alone or in combination of two or more.

In the present invention, as the catalyst component (C), only the component (C-1) may be used, or (C-
The component (2) may be used alone, or the component (C-1) and the component (C-2) may be used in combination. In the polymerization catalyst used in the present invention, if desired, as the component (D), a compound represented by the general formula (XIV) R ¹⁷ _m AlQ _3-m (XIV) [wherein R ¹⁷ is the same as the above, Q has 1 to 12 carbon atoms
Represents an alkyl group, an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and m is a number of 1 to 3. ] The organoaluminum compound represented by the following can be used. In particular,
(D) Organoaluminum compound when an ionic compound which reacts with the transition metal compound of the components (A) and (B) shown as the component (C-1) to form an ionic complex is used as the component (C). High activity can be obtained by using in combination.

Specific examples of the compound represented by the general formula (XIV) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, Examples include dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum sesquichloride. Next, in the present invention, at least one of the above (A), (B), (C) and (D) catalyst components used as desired can be used by supporting them on a suitable carrier.

The type of the carrier is not particularly limited,
An inorganic oxide carrier, any other inorganic carrier and an organic carrier can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. As the inorganic oxide carrier, specifically, SiO ₂ , Al ₂ O ₃ , MgO,
ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO,
Examples thereof include ZnO, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite and glass fiber. Among these, especially Si
O ₂ and Al ₂ O ₃ are preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.

On the other hand, as an inorganic carrier other than the above, MgC
Examples thereof include magnesium compounds such as l ₂ and Mg (OC ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ¹⁸ _i X ³ _j . here,
R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ³ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms,
i is 0 to 2, and j is 0 to 2. Further, examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene and polyarylate, starch and carbon. Here, the properties of the carrier used vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m.
² / g, preferably 50 to 500 m ² / g, a pore volume of usually 0.1 to 5 cm ³ / g, preferably 0.3~3cm ³ /
It is g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. In addition,
The specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method (see Journal of American Chemical Society, Volume 60, page 309 (1983)). Furthermore, it is desirable that the above-mentioned carrier is usually calcined at 150 to 1000 ° C, preferably 200 to 800 ° C before use. The method of loading on a carrier is not particularly limited, and a conventionally used method can be used. From the above,
By properly selecting the transition metal compound of the component (B), which contains the component (A), the component (B) and the component (C), an ethylene polymer having desired characteristics can be produced.

In the present invention, ethylene is homopolymerized in the presence of the above-mentioned polymerization catalyst, or ethylene is mixed with at least one selected from α-olefins having 3 to 20 carbon atoms, cyclic olefins, styrene and styrene derivatives. Copolymerization takes place. 3 to 20 carbon atoms to be copolymerized with ethylene
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-
Hexene, 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene and the like can be mentioned. The cyclic olefin has the general formula (X
V)

[0047]

[Chemical 12]

[Wherein, R ^{19 to} R ³⁰ each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and they may be the same or different from each other. And n represents an integer of 0 or more. ] The compound represented by these is mentioned. Examples of the cyclic olefin represented by the general formula (XV) include norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 5,5,6-trimethylnorbornene; 5
-Phenyl norbornene; 5-benzyl norbornene;
5-Ethylidene norbornene; 1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a, -octahydronaphthalene; 2-methyl-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a, -octahydronaphthalene; 2-cyclohexyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a,-
Octahydronaphthalene; 2,3-dichloro-1,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a, -octahydronaphthalene; 2-isobutyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a, -octahydronaphthalene; 1,2-dihydrodicyclopentadiene; 5-chloronorbornene;
5,5-dichloronorbornene; 5-fluoronorbornene; 5,5,6-trifluoro-6-trifluoromethylnorbornene; 5-chloromethylnorbornene; 5
-Methoxynorbornene; 5,6-dicarboxynorbornene anhydrate; 5-dimethylaminonorbornene; 5-cyanonorbornene; 2-ethyl-1,4.
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a, -octahydronaphthalene; 2,3-dimethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a, -octahydronaphthalene; 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a, -octahydronaphthalene; 2-ethylidene-1,4,5,8-dimethano-1,2,3,2
4,4a, 5,8,8a, -octahydronaphthalene;
2-fluoro-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a, -octahydronaphthalene; 1,5-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a, -octahydronaphthalene, etc. can be mentioned. Of these, norbornene and its derivatives are particularly suitable.

In addition to styrene, styrene derivatives such as p-methylstyrene, o-methylstyrene,
Also used as a comonomer is p-phenylstyrene. These comonomers may be used alone or in combination of two or more. In this polymerization,
(1) The case where the formation of the terminal vinyl group and the copolymerization reaction are independently present by the transition metal compound of the component (A) and the transition metal compound of the component (B), and (2) both reactions are the component (A). In some cases, it does not exist independently depending on the transition metal compound of (1) and the transition metal compound of the component (B).
The simultaneous presence of the transition metal compound of the component (A) and the transition metal compound of the component (B) in the polymerization reaction field enhances the non-Newtonian property of the produced polymer.

Control of the polymer structure, that is, non-Newtonian property can be performed by the component (A) component / (B) component molar ratio. The mixing ratio of the two components differs depending on the catalytic activity of each of the component (A) and the component (B) and cannot be unconditionally determined. However, in order to enhance the non-Newtonian property, the ratio of the component (A) is set. It is better to increase. Generally, the molar ratio of component (A) / component (B) is 1
/ 1000 to 1000/1, preferably 1/500 to 5
00/1, more preferably 1/300 to 300/1. The polymerization method in the present invention is not particularly limited, and is a solvent polymerization method using an inert hydrocarbon or the like (suspension polymerization, solution polymerization) or a bulk polymerization method in which polymerization is carried out in the presence of a substantially inert hydrocarbon solvent, gas A phase polymerization method can also be used.

Examples of the hydrocarbon solvent used in the polymerization include butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and other saturated hydrocarbons, benzene, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, chlorine-containing solvents such as chloroform, dichloromethane, ethylene dichloride and chlorobenzene. The polymerization temperature is usually -50 to
280 ° C, preferably 0 to 250 ° C, more preferably 1
It is selected in the range of 0 to 200 ° C., and the polymerization pressure is usually atmospheric pressure to
100 kg / cm ² G, preferably atmospheric pressure to 50 kg / c
m ² G, and more preferably from atmospheric pressure to 20 kg / cm ² G. The polymerization time is 0.1 second to 10 hours, preferably 1 second to 6 hours, more preferably about 1 minute to 5 hours. The composition can be controlled by an ordinary method based on the monomer charging ratio, and the molecular weight can be controlled by an ordinary method in which the polymerization temperature, the total monomer concentration, the catalyst concentration and the like are changed.

Next, the use ratio of each catalyst component in the present invention will be described. When using the components (1), (A), (B) and (C-1) as the catalyst components,
[(A) component + (B) component] / (C-1) component molar ratio is 1 / 0.1 to 1/100, preferably 1 / 0.5 to 1/1
It is desirable to use each component so as to be in the range of 0, more preferably 1/1 to 1/5. (2) When using the components (A), (B), (C-1) and (D), [(A) component + (B) component] / (C-1) component mole The ratio is the same as in the case of (1) above, but the [(A) component + (B) component] / (D) component molar ratio is from 1/2000 to.
It is preferably 1/1, preferably 1/1000 to 1/5, more preferably 1/500 to 1/10.
When (3) (A) component, (B) component and (C-2) component are used, [(A) component + (B) component] /
The molar ratio of component (C-2) is 1/10 to 1/10000, preferably 1/20 to 1/5000, more preferably 1 /
It is desirable to use each component so as to be in the range of 50 to 1/2000. (4) Component (A), component (B) and (C-
When the 2) component and the (D) component are used, the [(A) component + (B) component] / (C-2) component molar ratio is the above (3).
The same as the case of, but [(A) component + (B) component] /
The component (D) molar ratio is 1/2000 to 1/1, preferably 1/1000 to 1/5, and more preferably 1/500 to 1.
It is preferably in the range of / 10.

In the present invention, the following two-stage polymerization can be carried out. That is, in the catalyst system composed of (1) (B) component and (C) component, homopolymerization or copolymerization of ethylene is carried out to substantially produce a polymer, and then the (A) catalyst component is added and the polymerization is continued. Polymerize. This method makes it possible to control the molecular weight distribution and further change the branching degree distribution. Therefore, a molecular design corresponding to a wide range of required physical properties becomes possible. Further, in the two-step polymerization, the amount of carbon-carbon unsaturated bond of the produced copolymer is reduced, and an ethylene copolymer having improved thermal stability can be provided. On the other hand, in the one-step polymerization,
It has a relatively high amount of unsaturated groups and is suitable as a base material for chemically modified ethylene polymers. (2) In the method of (1) above, the component (B) of the first stage polymerization is used as the component (A),
It is possible to carry out the second-stage polymerization by changing the component (A) in the second-stage polymerization to the component (B).

The polymerization conditions in these two-step polymerizations are the same as in the case of the one-step polymerization, but taking the case of the above (1) as an example, regarding the catalyst charging conditions, the first step is the component (A). The component (B) and the component (B) may be replaced with the component (B), and in the second stage, the component (A) may be added and the component (A) and the component (C) may be added. Further, in the present invention, hydrogen treatment can be subsequently carried out after the completion of the polymerization reaction. In this hydrogen treatment, the unreacted monomer is removed or the hydrogen is left as it is at atmospheric pressure to 50 kg / cm.
^It may be introduced at a pressure of about ² G. Other conditions are the same as in the case of polymerization. This improves the thermal stability of the resulting polymer. The thus obtained ethylene-based polymer of the present invention has (a) a resin density of 0.86 to 0.97 g / ml, and (b) a maximum melting peak position that can be measured by a differential scanning calorimeter (DSC). Is 50 to 136 ° C
(C) The intrinsic viscosity measured in decalin at a temperature of 135 ° C. is 0.01 to 20 deciliter / g, and (d)
It is a non-Newtonian polymer having a ratio Mw / Mn of the weight average molecular weight (Mw) in terms of polyethylene and the number average molecular weight (Mn) measured by gel permeation chromatography of 2.0 to 40. Especially Mw
It is a polymer that can exhibit non-Newtonian properties even when / Mn is in the range of 2.0 to 6.0. This non-Newtonian property can be evaluated by a method based on the analysis of a molten fluid, a method based on the analysis of a polymer solution, and a method based on the relationship between the melt and the solution state. Next, the non-Newtonian evaluation method will be described.

(1) Method by Analysis of Melt Fluid The non-Newtonian property can be evaluated by the slope of the curve obtained from the relationship of the melt viscosity to the shear rate in the molten state. The large inclination indicates that the non-Newtonian property is excellent. Further, the flow characteristics can be examined by a capillary rheometer and evaluated by the activation energy (Ea) obtained from the shift factor.
Large non-Newtonian low density polyethylene (LDP
In E), Ea is about 12 kcal / mol, while in high density polyethylene (HDPE) it is 6 kcal / mo.
It is about 1.

(2) Method by analysis of polymer solution This can be evaluated from the relationship between the intrinsic viscosity [η] and the molecular weight obtained by gel permeation chromatography or light scattering method. The relationship between the intrinsic viscosity [η] determined from a diluted polyethylene solution using the Huggins equation and the molecular weight determined by gel permeation chromatography (GPC) method or light scattering method that determines the molecular weight according to the size of the solute polymer , It is known to reflect the branched structure of macromolecules. For example, the relationship between the intrinsic viscosity of linear HDPE and the molecular weight by the GPC method is different from that of LDPE having a long-chain branch, and when compared at the same intrinsic viscosity,
DPE has been shown to exhibit a lower molecular weight than HDPE. Reduced viscosity η _{SP / c} (deciliter / g),
Intrinsic viscosity [η] (deciliter / g), Huggins constant k
And the polymer concentration C (g / deciliter),
It is known that the relation of general formula (Huggins' formula) η _{SP / c} = [η] + k [η] ² C holds. The Huggins constant k is a value indicating the intermolecular interaction of the polymer in a dilute solution state, and is considered to be influenced by the molecular weight of the polymer, the molecular weight distribution, and the presence of branches. Introducing branching into the polymer structure has been shown to increase the Huggins constant in styrene / divinylbenzene copolymers [Journal of Polymer Sanence (J. Pol.
ymer Sci.) ", Volume 9, Page 265 (1952)
Year)〕. In addition, LDPE having a long chain branch and linear HDP
It has been shown that the Huggins constant of E is large in LDPE ["Polymer Handbook"]
Published by John Wiley Sons (1975)].

(3) Method based on relationship between melt and molten state Melt index of resin (M
The relationship between I) and the molecular weight (Mw) measured by the GPC method is different between linear polyethylene (HDPE) and non-Newtonian low density polyethylene (LDPE).
That is, HDPE shows a large Mw value with the same MI.

[0058]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of methylaluminoxane 200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) and trimethylaluminum were placed in a glass container having an inner volume of 500 ml and purged with argon. 24 ml (250
(Mmol) and added, and reacted at 40 ° C. for 8 hours. Then, toluene was distilled off under reduced pressure from the solution obtained by removing the solid component to obtain a catalyst product (methylaluminoxane).
6.7 g was obtained. The molecular weight of this product measured by the freezing point depression method was 610. Also, JP-A-62-3253
A high magnetic field component by ¹ H-NMR measurement based on Japanese Patent Publication No. 91-91, that is, when its proton nuclear magnetic resonance spectrum is observed in a toluene solution at room temperature, a methyl proton signal based on an “Al—CH ₃ ” bond is a tetramethylsilane standard. It is seen in the range of 1.0 to -0.5 ppm. The proton signal (0 ppm) of tetramethylsilane is "A
Since it is in the observation region based on the methyl proton based on the "1-CH ₃ " bond, the methyl proton signal based on the "Al-CH ₃ " bond is measured based on 2.35 ppm of the methyl proton signal of toluene in the tetramethylsilane standard. However, high magnetic field components (that is, -0.1 to -0.5p
pm) and other magnetic field components (that is, 1.0 to -0.1 ppm), the high magnetic field component was 43% of the whole.

[0059] (2) Preparation of the catalyst component (1,1 ^'- dimethylsilylene) ^(2,2' - isopropylidene) - bis production of (cyclopentadienyl) zirconium dichloride (1,1 ^'- dimethylsilylene) ( 2,2 ^'- isopropylidene) - bis (cyclopentadiene) 0.7 g (3.2
(48 mmol) in 30 ml of hexane, 6.48 mmol of n-butyllithium (1.5 mol / l hexane solution) was added dropwise to the mixture at -78 ° C, and the mixture was stirred at room temperature for 5 hours. Next, the solvent was distilled off, the residue was washed with 20 ml of hexane, and the white solid was dried under reduced pressure. Toluene suspension of this solid (20 ml)
0.8 g (3.2 mmol) of zirconium tetrachloride was added to, and the mixture was stirred at room temperature for 12 hours, then the solvent was distilled off, and recrystallization from dichloromethane / hexane was performed.
(1,1 ^'- dimethylsilylene) ^(2,2' - isopropylidene) - bis was obtained (cyclopentadienyl) zirconium dichloride 0.3g as a light yellow powder.

Of this thing¹When H-NMR was determined,
The following results were obtained.¹ H-NMR (90 MHz, CDCl₃): Δ1.01
[3H, s, (CH ₃) ₂Si], 0.54 [3H, s,
(CH ₃)₂Si], 1.52 (3H, s, (CH ₃)₂
C], 2.16 (3H, s, (CH ₃)₂C], 6.17
(2H, m, -CH-), 6.53 (2H, m, -CH
-), 6.82 (2H, m, -CH-) In addition, tetrahydro-4,4,8,8-tetramethyl-
4-ShiraS-Indacene says "Organo Metallics (O
rganometallics) Volume 10, 3739
Page (1991) ”.
It was (3) Polyethylene manufacturing method A pressure-resistant autoclave equipped with a 1-liter agitator was placed in a nitrogen atmosphere.
400 ml of toluene, triisobutyla under air
Luminium solution in toluene (2 mol / l) 0.25
Milliliter was added and stirred at 20 ° C. for 5 minutes. this
And 10 ml of the methylaluminoxane prepared in (1) above.
Rimol was added and the temperature was raised to 80 ° C. This is pentamethyl
−η^Five Of cyclopentadienyl titanium trimethoxide
Toluene solution (0.1 mol / l) 0.5 ml
And prepared in (2) above (1,1 ^'-Dimethyl silyl
(2)^'-Isopropylidene) -bis (cyclope
Ntadienyl) zirconium dichloride 0.002 mm
And then add ethylene at 6 kg / cm²With partial pressure of G
It was fed and the polymerization was started. 80 ° C with the total pressure kept constant
And reacted for 1 hour. After the reaction is completed, the pressure is released and the reaction product is meta
The polymer was recovered by pouring it into a nol and filtering it at 85 ° C.
It was dried under reduced pressure for 10 hours. As a result, polyethylene is 5.5
g was obtained.

(4) Analysis of polyethylene (a) Evaluation of thermal behavior The sheet obtained by hot pressing at 190 ° C. was used as a sample and measured by a DSC7 differential scanning calorimeter manufactured by Perkin Elmer. After melting for 5 minutes at 150 ℃, 10 ℃
The temperature was decreased to −50 ° C. at a rate of / min, and the crystallization enthalpy (Δ
H) was calculated. Further, the temperature was further raised at a rate of 10 ° C./min, and the melting point (Tm) was determined from the endothermic peak observed in this process. As a result, the crystallization enthalpy (ΔH) is 20.
The melting point (Tm) was 09.3 / g, and the melting point (Tm) was 129.3 ° C. (B) Measurement of Density A sample formed by hot pressing at 190 ° C. was used and measured by a density gradient tube method. As a result, the density was 0.962 g / ml. Moreover, the annealing treatment of the sample was not performed. (C) Molecular weight distribution measuring device: Waters ALC / GPC15C, column: Tosoh Corp., TSK HM + GMH6 × 2, solvent: 1,2,
The molecular weight was measured in terms of polyethylene by the GPC method under the conditions of 4-trichlorobenzene, temperature: 135 ° C., flow rate: 1 ml / min. As a result, the ratio Mw / Mn of the weight average molecular weight to the number average molecular weight was 16.2. (D) Measurement of intrinsic viscosity When the intrinsic viscosity in decalin at 135 ° C was determined, the intrinsic viscosity [η] was 0.98 deciliter / g.

[0062] In Example 1, (1,1 ^'- dimethylsilylene)
(2,2 ^'- isopropylidene) - bis instead of (cyclopentadienyl) zirconium dichloride, (1,
1 ^'- dimethylsilylene) ^(2,2' - dimethylsilylene) - except for using bis (cyclopentadienyl) zirconium dichloride was prepared of polyethylene in the same manner as in Example 1. The results are shown in Table 1.

[0063]

[Table 1]

[0064] Example 3 (1) (1,1 ^'- dimethylsilylene) ^(2,2' - isopropylidene) - bis (indenyl) zirconium dichloride magnesium in a 1-liter three-necked flask was prepared (a) nitrogen-substituted Lido 10.8 g and 45 ml of THF were added, and 0.6 ml of dibromomethane was added dropwise. After stirring for 5 minutes, the solvent was distilled off under reduced pressure, and 200 ml of THF was newly added. α, α'-dichloro-o-xylene 1
8.3 g (0.105 mol) was dissolved in 300 ml of THF and added dropwise at room temperature over 3 hours. After the completion of dropping, the mixture was stirred for 15 hours. The solution was cooled to -78 ° C and 6.8 g (36.2 mmol) of diethyl dimethylmalonate in THF was added.
The solution (100 ml) was added dropwise over 1 hour, the temperature was returned to room temperature, the mixture was stirred for 2 hours, and 100 ml of water was added at room temperature. The mixture was suction filtered, the solvent was evaporated under reduced pressure, and the mixture was extracted with dichloromethane and a 1N aqueous ammonium chloride solution. The organic layer was washed twice with water and dried over magnesium sulfate. The solid was filtered and the solvent was evaporated to give a yellow oil. Further, by purifying by column chromatography using activated alumina and recrystallizing with hexane, 4.8 g (15.9 mmol, yield: 44%) of the desired product (compound a below) as colorless crystals was obtained.
Obtained. When the ¹ H-NMR of this product was determined, the following results were obtained. ¹ H-NMR (CDCl ₃ , δ): 1.235 [s, 6H,
CH ₃ ), 3.02 (d, J = 16.4 Hz) and 3.
470 (d, J = 16.4 Hz) (8H, CH ₂ ), 3.7
67 (s, 2H, OH), 7.2-7.4 (mul, 8H,
PhH) Compound a

[0065]

[Chemical 13]

(Me represents a methyl group. The same shall apply hereinafter.) (B) 4.8 g (15.9 mmol) of compound a obtained in (a) was dissolved in 30 ml of dichloromethane, and p-
Toluenesulfonic acid (3.04 g, 15.9 mmol) was added and the mixture was refluxed for 8 hours. The reaction mixture was washed with aqueous sodium hydrogen carbonate solution and water, and dried over magnesium sulfate. The precipitate was filtered and the solvent was evaporated under reduced pressure to give a yellow oil. Purification by column chromatography using silica gel and recrystallization from hexane gave 2.3 g (8.6 mmol, yield: 54%) of the desired product (the following compound b) as colorless crystals. When the ¹ H-NMR of this product was determined, the following results were obtained. ¹ H-NMR (CDCl ₃ , δ): 1.586 [s, 6H,
CH ₃ ), 3.470 (s, 4H, CH ₂ ), 3.767
(S, 2H, CpH), 6.9 to 7.5 (mul, 8H, P
hH) Compound b

[0067]

[Chemical 14]

(C) A total of 6.2 g (22.7 mmol) of compound b obtained by repeating the above-mentioned reactions (a) and (b) in a Schlenk tube substituted with nitrogen and 50 parts of diethyl ether.
Added milliliters. The solution is cooled to -78 ° C and the concentration
28.4 ml (45.4 mmol) of 1.6 mol / l n-butyllithium was added dropwise. When the temperature was returned to room temperature, a white precipitate was gradually deposited. After stirring at room temperature for 3 hours, the supernatant was removed and the precipitate was washed twice with a small amount of diethyl ether. By drying under reduced pressure, a dilithium salt (compound c below) was obtained as a colorless powder. Compound c

[0069]

[Chemical 15]

(D) The dilithium salt (compound c) obtained above was dissolved in 100 ml of THF. Distilled dichlorodimethylsilane (3.0 g, 22.7 mmol) was slowly added dropwise at room temperature, and the mixture was stirred for 3 hours. The solvent was distilled off, the mixture was extracted with dichloromethane and water, and the organic layer was washed with water.
After washing twice, it was dehydrated with magnesium sulfate. The precipitate was filtered and recrystallized from hexane to give 6.5 g (19.6 mmol, yield: 86.5) of colorless crystals (compound d below).
%) Was obtained. When ¹ H-NMR of this product was obtained,
The following results were obtained. ¹ H-NMR (CDCl ₃ , δ): -0.354 [s, 6
H, SiCH ₃ ), 1.608 (s, 6H, CCH ₃ ),
3.347 (s, 2H, SiCH), 6.785 (s, 2
H, CpH), 6.9 to 7.6 (mul, 8H, PhH) Compound d

[0071]

[Chemical 16]

(E) Nitrogen-substituted Schlenk tube (D)
Then, 0.9 g (2.7 mmol) of the compound d obtained in 1. and 50 ml of hexane were added. Cool the solution to 0 ° C and concentrate
3.4 ml (5.4 mmol) of 1.6 mol / l n-butyllithium was added dropwise. When the temperature was returned to room temperature, a white precipitate was gradually deposited. After stirring at room temperature for 3 hours, the supernatant was removed and the precipitate was washed twice with hexane. By drying under reduced pressure, a dilithium salt (compound e below) was obtained as a pink powder. Compound e

[0073]

[Chemical 17]

(F) Toluene was added to the dilithium salt (compound e) obtained in (e) above to form a suspension solution. 630 mg of tetrachlorozirconium (2.7 mmol)
Was added dropwise at 0 ° C. Return to room temperature, 2
After stirring for 4 hours, the precipitate was filtered and the solution was concentrated.
By recrystallizing with toluene / hexane, 240 mg (0.508 mmol, yield: 19%) of yellowish yellow crystals were obtained. When the ¹ H-NMR of this product was determined, the following results were obtained. ¹ H-NMR (heavy THF, δ): -0.172 [s, 3
H, SiCH ₃ ), 0.749 [s, 3H, SiC
H ₃ ), 1.346 (s, 3H, CCH ₃ ), 2.141
(S, 3H, CCH ₃ ), 3.654 (s, 2H, Cp
H), 6.692 (s, 2H, CpH), 6.9 to 8.1 (m
ul, 8H, PhH) Zirconium complex

[0075]

[Chemical 18]

(2) Preparation of methylalnoxane Solid methylaluminum prepared in Example 1- (1)
Sun at 130 ℃, 3 × 10^-3At 5 o'clock under reduced pressure
It was heat treated for a while. Dissolve this in toluene and disperse
And (3) Production of ethylene / octene-1 copolymer 1 liter stainless steel autoclave under nitrogen stream
Dehydrated toluene 390 ml, dehydrated octene-1
10 ml and catalyst component 1 prepared in (2) above
Add millimolar (aluminum atom equivalent) and stir.
The temperature was raised to 65 ° C. I kept this state for 5 minutes
Pentamethylcyclopentadienyl titanium tri
(Sec-butoxide) 10 μmol, above (1)
Obtained with (1,1^'-Dimethylsilylene) (2,2^'
-Isopropylidene) -bis (indenyl) zirconium
Add 0.2 micromoles of mudichloride and heat up to 85 ℃
did. After that, 0.1 kg / cm of hydrogen²Introduce and pull G
Continuing ethylene 6kg / cm ²Guide for 60 minutes at a constant pressure of G
Continued to enter. After the polymerization reaction was completed, ethylene was depressurized and
The polymer was recovered by reprecipitation with a nol. Yield after drying under reduced pressure
Was 41.5 g. The results are shown in Table 2.

Example 4 360 ml of dehydrated toluene and dehydrated octene-1 were placed in a 1 liter stainless steel autoclave under a nitrogen stream.
40 ml, triisobutylaluminum (TI
BA) 1 mmol of (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride 2 micromolar, (1,1 ^'- dimethylsilylene) ^(2,2' - isopropylidene) - Bis (indenyl) zirconium dichloride (0.2 μmol) was charged, and the temperature was raised to 65 ° C. with stirring. Then, tetrakis (pentafluorophenyl) borate N, N
^' -Add 2.5 micromoles of dimethyl ammonium and add
The temperature was raised to 0 ° C., and ethylene was continuously introduced for 10 minutes at a constant pressure of 8 kg / cm ² G. After the completion of the polymerization reaction, ethylene was depressurized and the polymer was recovered by reprecipitation with methanol. After drying under reduced pressure, the yield was 62.5 g. The results are shown in Table 2. Example 5 360 ml of dehydrated toluene and dehydrated octene-1 were placed in a 1 liter stainless steel autoclave under a nitrogen stream.
40 ml and 6 mmol of methylaminoxane prepared in Example 1- (1) (in terms of aluminum atom) were charged. Then, (1,1 ^'- dimethylsilylene)
(2,2 ^'- isopropylidene) - bis (indenyl)
Zirconium dichloride (0.2 μmol) and ethylenebisindenyl zirconium dichloride (1 μmol) were added, and the temperature was raised to 85 ° C. 8 kg / cm of ethylene
^The introduction was continued for 10 minutes at a constant pressure of ² G. After the completion of the polymerization reaction, ethylene was depressurized and the polymer was recovered by reprecipitation with methanol. After drying under reduced pressure, the yield was 105 g. The results are shown in Table 2.

[0078]

[Table 2]

Example 6 (1) Preparation of catalyst Silica [Davison 952; manufactured by Fuji Devison Co., Ltd., trade name]
Was added for 48 hours at 400 ° C. to water (1.8 g) to prepare a silica carrier having a water content of 4.86 wt%. 2.82 g of this carrier was dissolved in 25 ml of toluene, and methylaluminoxane [manufactured by Ethyl Corporation] 2
It was added to 0 mmol with stirring at 0 ° C. for 1 hour. After further stirring for 1 hour, the mixture was stirred at 80 ° C. for 2 hours. Next, the solvent toluene is distilled off, and the solvent is heated at 100 ° C. for 2 hours.
It was dried under reduced pressure for an hour. This was redispersed in hexane, and cyclopentadienyl titanium trimethoxide.
8 mmol and (1,1 ^'- dimethylsilylene) (2,
2 ^'- isopropylidene) - stirring the mixed toluene Solution 5 ml of bis (indenyl) zirconium dichloride 16 micromoles, was added dropwise over a period 10 minutes at room temperature and stirred for an additional 1 hour. As a result, a supported catalyst was obtained in which the solution portion was colorless and transparent and the slurry portion was ocher. (2) Production of ethylene / octene-1 copolymer In a 1 liter stainless steel autoclave, 400 ml of dehydrated hexane and 400 ml of dehydrated octene under a nitrogen stream.
4 ml and 3 mmol of methylaminoxane prepared in Example 3- (2) (in terms of aluminum atom) were charged. Next, 1.25 ml of the catalyst component prepared in (1) above was added and the temperature was raised to 80 ° C. Further, ethylene was continuously introduced at a constant pressure of 4 kg / cm ² G for 60 minutes. After the completion of the polymerization reaction, ethylene was depressurized and the polymer on the particles was recovered. After drying under reduced pressure, the yield was 12.5 g.
The melting point of this product was 116 ° C and the density was 0.920 g /
It was cm ³ .

[0080]

EFFECTS OF THE INVENTION According to the present invention, the molecular weight distribution, which is a characteristic of metallocene catalysts, is controlled and, in addition, it has non-Newtonian properties, good film moldability and blow moldability are imparted, and molding processing is performed. It is possible to obtain an ethylene-based polymer with high energy efficiency and low cost and high-speed moldability at high efficiency.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuhiro Yabunouchi, 1280, Kamizumi, Sodegaura, Chiba Prefecture, Idemitsu Kosan Co., Ltd. (72) Masami Watanabe, 1280, Kamizumi, Sodegaura, Chiba, Idemitsu Kosan, Ltd. 56) References JP-A-3-203904 (JP, A) JP-A-3-203914 (JP, A) JP-A-62-121709 (JP, A) JP-A-62-153307 (JP, A) JP-A Flat 7-102013 (JP, A) International publication 93/020113 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (8)

(57) [Claims] 1. (A) General formula (II): (In the formula, M represents a metal element of Group 4 of the periodic table, E ¹ and E ² are each a π-bonding ligand, and (A ¹ ) _p
And (A ² ) _p to form a crosslinked structure, and they may be the same or different from each other, and X is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a carbon number of 1 to 1
20 represents a σ-bonding ligand selected from 20 alkoxy groups, and when there are plural X's, the plural X's may be the same or different and are cross-linked with other X, E ¹ , E ² or Y. May be. Y represents a Lewis base, A ¹ and A ² are respectively (In the formula, R ¹ and R ² are a hydrogen atom and a halogen atom, respectively.
Child, hydrocarbon group having 1 to 20 carbon atoms, ha group having 1 to 20 carbon atoms
Rogen-containing hydrocarbon group, silicon-containing group or hetero atom-containing
Groups, which may be the same or different,
They may be bonded to each other to form a ring structure. _{), R '2 Si, R} ' 2 Ge, R ' in ₂ Sn (wherein, R' is hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, charcoal
Halogen-containing hydrocarbon group having a prime number of 1 to 20, silicon-containing group or
Is a heteroatom-containing group, and when R ′ is 2
May be the same as or different from each other, and may be linked to each other to form a ring.
It may form a structure. Represents a cross-linking group selected from among these, which may be the same or different from each other, but at least one of them is composed only of a cross-link by carbon. p is an integer of 1 to 4, each p may be the same or different, and q is an integer of 1 to 5 [(valence of M)]
-2] and r is 0. ] And a compound capable of forming an ionic complex from (B) another transition metal compound and (C) component (A) and component (B) or a derivative thereof. (However, the transition metal compound of the component (B) is
A compound containing a metal belonging to Groups 10 to 10 or a lanthanoid series metal is shown. ) In the presence of ethylene homopolymerization,
Alternatively, a method for producing an ethylene polymer, which comprises copolymerizing ethylene with at least one selected from α-olefins having 3 to 20 carbon atoms, cyclic olefins, styrene and styrene derivatives. 2. Homopolymerization of ethylene, or C3 to C3 in the presence of a catalyst composed of component (B) and component (C).
After copolymerizing ethylene with at least one selected from the group consisting of 20 α-olefins, cyclic olefins, styrene and styrene derivatives, a polymer is formed substantially, and then (A) a catalyst component is added to carry out polymerization. The method for producing an ethylene polymer according to claim 1, which is carried out. 3. Ethylene homopolymerization or carbon number 3 to 3 in the presence of a catalyst composed of components (A) and (C).
After copolymerizing ethylene with at least one selected from the group consisting of 20 α-olefins, cyclic olefins, styrene and styrene derivatives, a polymer is produced substantially, and then the polymerization is carried out by adding the catalyst component (B). The method for producing an ethylene polymer according to claim 1, which is carried out. 4. The transition metal compound of component (A) is titanium,
One or more compounds containing a metal selected from zirconium and hafnium, wherein the transition metal compound of component (B) is titanium, zirconium, hafnium, chromium,
The method for producing an ethylene polymer according to claim 1, which is one or more compounds containing a metal selected from vanadium and lanthanoid series. 5. The transition metal compound as the component (B) is a transition metal compound having a π ligand or a transition metal compound having a σ-bonding ligand, a chelating ligand or a Lewis base ligand. The method for producing an ethylene polymer according to claim 1. 6. The method for producing an ethylene polymer according to claim 1, wherein a catalyst in which at least one selected from the components (A), (B) and (C) is supported on a carrier is used. 7. After the polymerization reaction, ethylene polymer The method according to any one of claims 1 to 6 for continued hydrogen treatment. 8. The ethylene polymer (a) has a resin density of 0.86 to 0.97 g / ml.
(B) The maximum melting peak position that can be measured by a differential scanning calorimeter is in the range of 50 to 136 ° C., or it does not substantially show a melting peak, (c) measured in decalin at a temperature of 135 ° C. Has an intrinsic viscosity of 0.01 to 2
0 dL / g, and (d) the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography is 2.0 to 40. method for producing an ethylene polymer according to any one at which of claims 1-7 which is in the range.