JP3489786B2 - Method for producing ethylene polymer and ethylene polymer obtained by the method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an ethylene polymer and a novel ethylene polymer obtained by the method. More specifically,
INDUSTRIAL APPLICABILITY The present invention is an ethylene-based product which has improved non-Newtonian property, is provided with good film moldability and blow moldability, and has low energy and cost reduction in molding process, and has been imparted with high-speed moldability. A method for producing a polymer with high efficiency, an ethylene polymer having the above-mentioned preferable properties obtained by this method, or an ethylene polymer having a preferable property as an elastomer, that is, a high-density polyethylene phase as a hard segment, It has a crystalline phase such as a tactic polypropylene phase, an isotactic polystyrene phase, a syndiotactic polystyrene phase, an amorphous frozen phase mainly composed of cyclic olefin units, and a soft segment consisting of a copolymer phase with ethylene. As a thermoplastic elastomer or a thermoplastic heat resistant elastomer It relates Useful ethylene polymer.

[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, the polyolefin obtained by using the metallocene-based catalyst has a poor processing property due to a narrow molecular weight distribution, and as a result, has a drawback in that it cannot avoid a large limitation in film molding (inflation molding) or blow molding. ing.

On the other hand, a method for producing an ethylene-based polymer by using a constrained geometry type catalyst and an ethylene-based polymer obtained by the method have been disclosed (JP-A-3-163088).
No.), and the copolymer obtained by this method exhibits non-Newtonian properties and improves processability. However, the processing characteristics are still insufficient,
Not always satisfactory. Further, in order to impart non-Newtonian property, it is considered to introduce a long chain branch, but a performance and an efficient introduction method for practical use have not been obtained yet. To introduce a long-chain branch, it is easy to generate a vinyl group and the reactivity between the vinyl group and the monomer is good, that is, the copolymerizability is good.
There are two conditions, but the fact is that no catalyst and polymerization method satisfying these two conditions at the same time have been found so far. By satisfying these two conditions at the same time, it becomes possible to produce a polymer into which long chain branching has been introduced under extremely mild conditions.

[0004]

Under these circumstances, the present invention has improved non-Newtonian properties, imparts good film moldability and blow moldability, and reduces energy consumption during molding. And a method for producing an ethylene polymer at low cost and having high-speed moldability with high efficiency, useful as an ethylene polymer or a thermoplastic elastomer having the above-mentioned preferable properties obtained by this method The purpose of the present invention is to provide an ethylene-based polymer and a thermoplastic resin composition containing the ethylene-based polymer.

[0005]

Means for Solving the Problems The present inventors have
As a result of repeated studies to achieve the specific polymerization temperature
Of ethylene by a multi-stage polymerization method using the temperature conditions and the catalyst.
Homopolymerization of ethylene, or ethylene and ethylenic addition polymerization monomer
The non-Newtonian property is improved by copolymerization with
An ethylene-based polymer having the above-mentioned preferable properties
Ethylene-based polymers useful as ruby or thermoplastic elastomers
It was found that coalescence was obtained. The present invention provides such knowledge
It was completed based on. That is, the present invention is
(A) metal compound having terminal vinyl group-forming ability, and
(B) an ionic complex from the metal compound or its derivative
Multistage polymerization using a catalyst whose main component is a compound that can be formed
Method ethylene homopolymer or ethylene and ethylenic
In producing a copolymer with an addition polymerization monomer,
(1) Polymerization temperature T₁And T ₂In ethylene and oct
Copolymerization molar ratio with ten-1 [octene-1 / (eth
Len + octene-1)]
Melting point (Tm) of ren / octene-1 copolymer and crystallization energy
The product with the enthalpy (ΔH) is (Tm)^T1・ (ΔH)^T1> (Tm)^T2・ (ΔH)^T2 [However, (Tm)^T1And (ΔH)^T1Is the polymerization temperature
Degree T₁Of ethylene / octene-1 copolymer synthesized in
Points and enthalpies of crystallization, (Tm)^T2And (Δ
H)^T2Is the polymerization temperature T₂Ethylene synthesized in
Shows melting point and enthalpy of crystallization of cutene-1 copolymer
You ], And (2) Smell of (1) above
The polymerization temperature T₂Ethylene / octene-1 synthesized in
Melting point of polymer (Tm)^T2And enthalpy of crystallization (ΔH)
^T2The product of and is the expression 0 ≦ (Tm)^T2・ (ΔH)^T2≤27,000-21600
[M]^0.56 Adopt a polymerization temperature condition and a catalyst that simultaneously satisfy the relationship of
The polymerization temperature of the first stage to T ₁And the second stage polymerization temperature
T₂For producing an ethylene-based polymer characterized by
And an ethylene-based polymer produced by the method
And (a) the resin density is 0.86-0.97g / milliliter
Torr, (b) measured by a differential scanning calorimeter
Maximum melting peak position is in the range of 50-270 ° C
That it does not exhibit a melting peak.
Or exhibiting multiple independent melting peaks, (C)
The intrinsic viscosity measured in decalin at a temperature of 135 ° C is 0.01.
~ 20 deciliters / g, and (d) gelpa
Porosity measured by permeation chromatography
Weight average molecular weight (Mw) and number average molecule in terms of ethylene
Ratio Mw / Mn with amount (Mn) is in the range of 2.0-40
Ethylene polymer characterized by the above, and the ethylene
To provide a thermoplastic resin composition containing a base polymer
Is. In the present invention, as the polymerization catalyst, terminal vinyl chloride is used.
(1) Polymerization temperature T₁
And T₂Copolymerization of ethylene with octene-1
Charge molar ratio [octene-1 / (ethylene + octene-
1)] Ethylene / octene produced when M is equalized
1 Melting point (Tm) of copolymer and enthalpy of crystallization (Δ
H) is the product of (Tm)^T1・ (ΔH)^T1> (Tm)^T2・ (ΔH)^T2 [However, (Tm)^T1And (ΔH)^T1Is the polymerization temperature
Degree T₁Of ethylene / octene-1 copolymer synthesized in
Points and enthalpies of crystallization, (Tm)^T2And (Δ
H)^T2Is the polymerization temperature T₂Ethylene synthesized in
Shows melting point and enthalpy of crystallization of cutene-1 copolymer
You ], And (2) Smell of (1) above
The polymerization temperature T₂Ethylene / octene-1 synthesized in
Melting point of polymer (Tm)^T2And enthalpy of crystallization (ΔH)
^T2The product of and is the expression 0 ≦ (Tm)^T2・ (ΔH)^T2≤27,000-21600
[M]^0.56 Those that satisfy the relationship of are used at the same time. like this
As the polymerization catalyst, (A) a metal compound and (B) the metal
Compound capable of forming ionic complex from compound or its derivative
Those containing a compound as a main component are mentioned.

As the metal compound used as the component (A), various compounds can be mentioned, and the general formula CpM ¹ R ¹ _a R ² _b R ³ _c (I) Cp ₂ M ¹ R ¹ _{a ^{R 2 b ··· (II) (}} Cp-A e -Cp) M 1 R 1 a R 2 b ··· (III) or general formula _{^{M 1 R 1 a R 2 b}} R 3 c R 4 d ·· The compound represented by (IV) and its derivatives are preferable. In the general formulas (I) to (IV), M ¹ represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium, or chromium, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group. , A substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group, a substituted fluorenyl group, and the like cyclic unsaturated hydrocarbon group or chain unsaturated hydrocarbon group. R ¹ , R ² , R ³ and R ⁴ are independently σ
A binding ligand, a chelating ligand, a Lewis base, and other ligands are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon number of 1. ~ 20
Alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, alkylaryl group or arylalkyl group, C1-C20 acyloxy group,
Examples thereof include an allyl group, a substituted allyl group, and a substituent containing a silicon atom, and examples of the chelating ligand include an acetylacetonate group and a substituted acetylacetonate group. A indicates crosslinking by covalent bond. a, b,
c and d each independently represent an integer of 0 to 4, and e represents an integer of 0 to 6. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other.

Substituted cyclohexyl in the above formulas (I) to (III)
Examples of the pentadienyl group include methylcyclopenta
Dienyl group, ethylcyclopentadienyl group; isopro
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
Examples thereof include a tadienyl group. In addition, the above (I)
R in formula (IV) ¹~ R^FourFor example,
Fluorine atom, chlorine atom, bromine atom as halogen atom,
Iodine atom, methyl as an alkyl group having 1 to 20 carbon atoms
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, octyl group, 2-ethylhexyl group, carbon number
Methoxy group and ethoxy as the alkoxy group of 1 to 20
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl group, tolyl group, xylyl as reel alkyl group
Group, benzyl group, and acyloxy group having 1 to 20 carbon atoms
The heptadecylcarbonyloxy group and silicon atom.
Trimethylsilyl group as a substituent, (trimethylsilyl group
) Methyl group, dimethyl ether as a Lewis base, di-
Ethers such as ethyl ether and tetrahydrofuran
, Thioethers such as tetrahydrothiophene,
Esters such as tylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethyl
Luaniline; pyridine; 2,2'-bipyridine; phena
Amines such as nitroline, triethylphosphine;
Phosphines such as Liphenylphosphine, chain unsaturated
As hydrocarbons, ethylene; butadiene; 1-pente
Isoprene; Pentadiene; 1-Hexene and this
As a derivative thereof, as a cyclic unsaturated hydrocarbon, benzene;
Ruene; Xylene; Cycloheptatriene; Cyclooctane
Tadiene; Cyclooctatriene; Cyclooctatetra
Examples thereof include ene and derivatives thereof. Also, above
Examples of the covalent cross-linking of A in the formula (III) include
For example, methylene bridge, dimethylmethylene bridge, ethylene
Cross-linked, 1,1'-cyclohexylene cross-linked, dimethylsilyl
Lene cross-link, dimethyl germylene cross-link, dimethyl stannile
And cross-linking.

Examples of the compound represented by the general formula (I) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl). Tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadiene (Enyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconi , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, Among these, compounds in which zirconium is replaced with titanium or hafnium are mentioned.

Examples of the compound represented by the general formula (II) include bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis ( Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethane Cyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) dichlorozirconium and the like, as well as compounds in which zirconium is replaced with titanium or hafnium.

Examples of the compound represented by the general formula (III) 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 (IV) include tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t -Butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), and the like, and compounds in which zirconium is replaced with titanium or hafnium. Specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium. , Dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium dichloride, dicyclopentadienylmethyl vanadium and the like.

Specific examples of the chromium compound include tetramethyl chromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) chromium, hydrido tricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclo Examples include pentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like. further,
As the components (A) and (B), in the general formula (III), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). A group 4 transition metal compound having a multicoordinating compound bonded to each other through an element selected from group 14 of the periodic table as a ligand can be preferably used. Examples of such compounds include those represented by the general formula (V)

[0013]

[Chemical 1]

The compounds represented by
be able to. Y in the general formula (V)¹Is carbon, Kei
Element, germanium or tin atom, R^Five _t-C_FiveH_4-tOver
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u represent an integer of 1 to 4. Where R^Five
Are hydrogen atoms, silyl groups or hydrocarbon groups,
It may be one or different. Also, at least one piece
The other cyclopentadienyl group is Y¹Is bound to
R on at least one carbon next to the carbon^FiveExists.
R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group of formula 6 to 20, an alkylaryl group or
Indicates an arylalkyl group. M²Is titanium, zirconium
Or a hafnium atom, X¹Is a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or aryl group of
It shows a alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹R may be the same or different from each other, and R⁶Also
They may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (V) include a methylcyclopentadienyl group; an ethylcyclopentadienyl group; an isopropylcyclopentadienyl group; a 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, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group and a benzyl group.

Specific examples of the compound represented by the general formula (V) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2,3,5-trimethyl). Examples thereof include cyclopentadienyl) titanium dichloride and dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride. Furthermore, general formula (VI)

[0017]

[Chemical 2]

It also includes compounds represented by: The general formula
In the compound of (VI), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. M³Is titanium, zirconium or hafni
X represents a um atom²Is hydrogen atom, halogen atom, carbon
C1-C20 alkyl group, C6-C20 aryl
Group, alkylaryl group or arylalkyl group, or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is Si
R⁷ ₂, CR⁷ ₂, SiR⁷ ₂SiR⁷ ₂, CR⁷ ₂CR⁷ ₂, CR
⁷ ₂CR⁷ ₂CR⁷ ₂, CR⁷= CR⁷, CR⁷ ₂SiR⁷ ₂Or
GeR⁷ ₂Indicates Y ²Is -N (R⁸)-, -O-, -S-
Or -P (R⁸) -Indicates. R above⁷Is a hydrogen atom or 2
Alkyl, aryl, silyl having up to 0 non-hydrogen atoms
And alkyl halides, aryl halides and
R is a group selected from these combinations,⁸Has 1 to 1 carbon atoms
An alkyl group having 10 or an aryl group having 6 to 10 carbon atoms
Yes, or one or more R⁷And up to 30
May form a fused ring system of non-hydrogen atoms. w is 1 or
2 is shown.

Specific examples of the compound represented by the above general formula (VI) 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.

In the present invention, the same metal compound is usually used to carry out multi-stage polymerization under different temperature conditions. However, if the polymerization conditions of the present invention are satisfied under different temperature conditions, each stage is different. Metal compounds can also be used. In the polymerization catalyst of the present invention, the metal compound as the component (A) may be used alone or in combination of two or more kinds. On the other hand, in the polymerization catalyst, (B)
Examples of the compound used as a component that can form an ionic complex from the metal compound of the component (A) or a derivative thereof include (B-1) an ionic compound that reacts with the metal compound of the component (A). An ionic compound forming a complex, (B-
2) Aluminoxane can be illustrated. The (B
As the compound of the component -1), any ionic compound that can react with the metal compound of the component (A) to form an ionic complex can be used, but the cation and the plurality of groups are elements. A compound composed of an anion bonded to the above, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bonded to an element can be preferably used.
Examples of the compound such cations and a plurality of groups consisting of bound anions to elemental general formula ([L ¹ -R ^{9] k +)} _p ^{([M 4 Z 1 Z 2 ·· Z} n ] ^{(hg) -} ) _Q ·· (VII) or ([L ² ] ^{k +} ) _p ([M ⁵ Z ¹ Z ² ·· Z ⁿ ] ^(hg)- ) _q ·· (VIII) (where L ² is M ⁶ , R ¹⁰ R ¹¹ M ⁷ , R ¹² ₃ C or R ¹³
M ⁷ ) (wherein L ¹ is a Lewis base, M ⁴ and M ⁵ are, respectively, groups 5, 6, 7, 8-10, 11 and 12 of the periodic table.
An element selected from Group 13, 13, 14 and 15 groups, preferably an element selected from Group 13, 14 and 15 groups, M
⁶ and M ⁷ are the 3rd, 4th, 5th, and 6th groups of the periodic table, respectively.
An element selected from Group 7, Group 7, 8-10, Group 1, 11, Group 2, 12 and Group 17, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, and an alkoxy group having 1 to 20 carbon atoms, respectively. Group, aryloxy group having 6 to 20 carbon atoms, 1 to carbon atoms
20 alkyl group, C 6-20 aryl group, alkylaryl group, arylalkyl group, C 1-20
Represents a halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group or a halogen atom,
¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁹ 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 ¹⁰ and R ¹¹ respectively represent a cyclopentadienyl group and a substituted cyclopenta group. Dienyl group, indenyl group or fluorenyl group, R ¹² has 1 carbon atom
To 20 alkyl groups, aryl groups, alkylaryl groups or arylalkyl groups. R ¹³ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. g is an valence of M ⁴ and M ⁵ and is an integer of 1 to 7, and h is 2
8 is an integer, k is an ionic valence of [L ¹ -R ⁹ ], [L ² ] and is an integer of 1 to 7, p is an integer of 1 or more, q = (p × k) /
(H-g). ) Is a compound represented by.

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 ⁴ and M ⁵ ,
Specific examples of B, Al, Si, P, As, Sb, and preferably B or P, M ⁶ include Li, Na, Ag, and C.
Specific examples of M ⁷ , 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 ⁹ and R ¹² include the same as those mentioned above.
Specific examples of the substituted cyclopentadienyl group for R ¹⁰ and R ¹¹ 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, and the number of substituted alkyl groups is an integer of 1 to 5.

Among the compounds of the above general formulas (VII) and (VIII), those in which M ⁴ and M ⁵ are boron are preferable. Among the compounds of the general formulas (VII) and (VIII), the following compounds can be used particularly preferably. For example, as the compound of the general formula (VII), tetraethylborate triethylammonium, tetraphenylborate tri (n-butyl) ammonium, tetraphenylborate trimethylammonium, tetraphenylborate tetraethylammonium, tetraphenylborate methyltri (n-butyl) is used. 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, tetrakis (pentafluorophenyl) methyltriphenylammonium borate, te Rakisu (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 (VIII),
Ferrocenium tetraphenylborate Tetrasilver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) ferrocenium borate, tetrakis (pentafluorophenyl) borate (1,1'-dimethylferroate) Cerium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, cyanoferrotetrakis (pentafluorophenyl) borate Cenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithi tetrakis (pentafluorophenyl) borate Um, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetrakis (pentafluorophenyl) boric acid (tetraphenyl) Porphyrin zinc), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate, and the like. In addition, as compounds other than the general formulas (VII) and (VIII), for example, tris (petafluorophenyl) boric acid, tris [3,5-di (trifluoromethyl) phenyl] boric acid, triphenylboric acid, etc. are also used. can do.

As the component (B-1), one type of ionic compound which reacts with the metal compound of the component (A) to form an ionic complex may be used, or two or more types may be used in combination. Good. Further, the component composed of the metal compound of the component (A) and the ionic compound capable of forming the ionic complex of the component (B-1) may be a polycation complex. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (IX)

[0026]

[Chemical 3]

(In the formula, R ¹⁴ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, which may be the same or different. s represents the degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40. ) A chain aluminoxane represented by the general formula (X)

[0028]

[Chemical 4]

The cyclic aluminoxane represented by the formula (wherein R ¹⁴ and s are the same as above) can be mentioned. Among the compounds of the general formulas (IX) and (X), 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, modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the general formulas (IX) and (X) with a compound having active hydrogen such as water can also be preferably used.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be carried out according to a known method. For example, an organoaluminum compound is dissolved in an organic solvent, a method of bringing it into contact with water, a method of initially adding an organoaluminum compound during polymerization, and a method of adding water later, water of crystallization contained in a metal salt, There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. These aluminoxanes may be used alone or in combination of two or more.

In the present invention, as the catalyst component (B), only the component (B-1) may be used, or (B-
The component (2) may be used alone, or the component (B-1) and the component (B-2) may be used in combination. Further, as the catalyst component (B), a Lewis acid can be used as the electron pair acceptor other than the components (B-1) and (B-2). Here, the Lewis acid is not particularly limited as long as it has a function of coordinating to and stabilizing a metal cation. Such compounds include metal oxides, metal halides, and the like, and as the metal species, particularly aluminum,
Boron, zinc, tin, magnesium, antimony, silicon, calcium, gallium, manganese, iron, cobalt,
Examples include nickel. In the polymerization catalyst used in the present invention, if desired, as the component (C), a compound represented by the general formula (XI) R _r AlQ _3-r ... (XI) (wherein R is an alkyl group having 1 to 12 carbon atoms) , Q represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is a number of 1 to 3.) can be used. In particular, when an ionic compound which reacts with the metal compound of the component (A) shown as the component (B-1) to form an ionic complex is used as the component (B), the organoaluminum compound (C) is used in combination. Thus, high activity can be obtained.

Specific examples of the compound represented by the general formula (XI) 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, the above (A),
At least one of (B) and the (C) catalyst component used as desired can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers 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, Zr
O ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Zn
Examples include O, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Among these, especially SiO ₂ , A
1 ₂ O ₃ is 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 ¹⁵ _i X ³ _j . here,
R ¹⁵ 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. Examples of the organic carrier include polystyrene, polyethylene, polypropylene, substituted polystyrene, polymers such as 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
It is 200 μm, more preferably 20 to 100 μm.

When the particle size is small, the amount of fine powder in the polymer increases,
If the particle size is large, coarse particles in the polymer increase, which causes a 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, pore volume is usually 0.1-5 cm ³ / g,
It is preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume are
For example, it can be determined from the volume of nitrogen gas adsorbed according to the BET method (Journal of American
See Chemical Society, Volume 60, page 309 (1983)). Further, the carrier is usually 15
It is desirable to use by firing at 0 to 1000 ° C, preferably 200 to 800 ° C. The method of loading on a carrier is not particularly limited, and a conventionally used method can be used. From the above catalyst group, it is possible to produce an ethylene-based polymer having desired characteristics by containing the components (A) and (B) as essential components and appropriately selecting the metal compound of the component (A). it can. Next, the usage ratio of each catalyst component in the present invention will be described. When the components (1), (A) and (B-1) are used as catalyst components, the molar ratio of component (A) / component (B-1) is 1
/0.1 to 1/100, preferably 1 / 0.5 to 1/10,
It is more desirable to use both components so as to be in the range of 1/1 to 1/5. (2) Component (A) and (B-
When the component (1) and the component (C) are used, the molar ratio of the component (A) / the component (B-1) is the same as that of the above (1), but the component (A) / the component (C) is used. The molar ratio is 1 / 2000-
It is preferably 1/1, preferably 1/1000 to 1/5, more preferably 1/500 to 1/10.
When (3) component (A) and component (B-2) are used, the molar ratio of component (A) / component (B-2) is 1/20.
~ 1/10000, preferably 1/100 to 1/500
It is desirable to use both components so as to be in the range of 0, more preferably 1/200 to 1/2000. (4) (A)
When the component, the component (B-2) and the component (C) are used, the component (A) component / (B-2) component molar ratio is the same as in the case of the above (3), but the component (A) is used. / (C) component molar ratio is 1/2000 to 1/1, preferably 1/1000 to 1 /
5, more preferably 1/500 to 1/10. In addition, the polymerization form is not particularly limited, and a solvent polymerization method using an inert hydrocarbon (turbid polymerization, solution polymerization) or a bulk polymerization method in which polymerization is performed in the absence of a substantially inert hydrocarbon solvent, a gas phase Examples of the hydrocarbon solvent used in the polymerization that can be used in the polymerization method include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, and aromatics such as benzene, toluene and xylene. Group hydrocarbons, chloroform, dichloromethane,
Examples include chlorine-containing solvents such as ethylene dichloride and chlorobenzene. The polymerization temperature is generally 0 to 250 ° C., and the polymerization pressure is generally atmospheric pressure to 150 kg / cm ² , but preferably 10 to 220 ° C. and atmospheric pressure to 100.
kg / cm ² More preferably 15 to ²⁰⁰ ° C., normal pressure to
It is in the range of 90 kg / cm ² . The molecular weight of the obtained polymer may be controlled by a commonly used method. For example, it can be controlled by temperature, monomer concentration, catalyst concentration and the like. The ethylene-based polymer of the present invention produces a terminal vinyl group at a polymerization temperature T ₁ in ethylene homopolymerization or copolymerization of ethylene and an ethylenic addition-polymerized monomer,
In addition, it is obtained by reacting a catalyst having a copolymerizability in a specific range at the polymerization temperature T ₂ . The ethylene polymer of the present invention has a non-Newtonian property,
Probably due to the presence of long chain branching.

Next, the formation and copolymerizability of terminal vinyl groups will be described. (A) Generation of terminal vinyl group Generally, in the polymerization system involving ethylene or propylene, the formation of the terminal vinyl group is caused by β hydrogen and β at the growth terminal.
It is said to be generated by elimination chain transfer of an alkyl group.
Whether or not the catalyst has the ability to generate a terminal vinyl group can be determined by evaluating a polymer produced by carrying out ethylene polymerization or copolymerization using the metal compound (A) and aluminoxane. However, when the production amount is small, it is necessary to adopt polymerization conditions for lowering the molecular weight, such as increasing the catalyst concentration and decreasing the monomer concentration. As a method for quantifying the terminal vinyl group, IR measurement shows 907 cm.
^From the peak of the terminal vinyl group appearing at ^-1 , the number n of terminal vinyl groups per 100 carbons is calculated by the formula n = 0.114 × A ₉₀₇ / (D × T) [A ₉₀₇ : Absorbance at ₉₀₇ cm ⁻¹ , D : Density (g / milliliter), T: measurement film thickness (mm)] can be used.

The one having a large number of terminal vinyl groups thus obtained, that is, the one preferably used as the metal compound as the component (A), is a compound containing a metal such as titanium, zirconium, hafnium or vanadium. be able to. Moreover, it can be said that the number of terminal vinyl groups generally indicates the ease with which vinyl groups are formed. This is because the number of vinyl groups will eventually decrease in the case of a catalyst in which vinyl groups are easily generated and the vinyl groups and monomers are easily reacted to form branches. On the other hand, a large number of vinyl groups remain in a catalyst that easily forms vinyl groups and has poor copolymerizability. Therefore, it is necessary to look at the easiness of branch generation. This is gel permeation chromatography (GP
C) Polyethylene-equivalent number average molecular weight M determined from measurement
n and the number average molecular weight Mn obtained from the ratio of the main chain methylene and the terminal group by H-NMR measurement can be evaluated. When evaluating branching based on this Mn ratio, (1)
In Mn obtained by GPC measurement, when it has a branched structure,
It does not necessarily indicate the true molecular weight. (2) It is necessary to comprehensively judge and quantify, taking note that the accuracy of the Mn value decreases when the molecular weight distribution is wide.

(B) Copolymerizability A high degree of copolymerizability is required to copolymerize the produced terminal vinyl group with ethylene or another comonomer. In particular, the copolymerizability of higher α-olefins is generally extremely reduced as the number of carbon atoms increases and the proportion of vinyl groups per molecular weight decreases. In the present invention, the monomer composition ratio [octene-1 / (ethylene + octene-1) molar ratio [M]] at the polymerization temperature T ₂ , the crystallization enthalpy (ΔH) ^T2 and the melting point (Tm) of the produced copolymer. The relation with the product of ^T2 is expressed by the formula 0 ≦ (ΔH) ^T2 · (Tm) ^T2 ≦ 27000-21600
Ethylene / octene-1 obtained by satisfying [M] ^0.56 and obtaining the same molar ratio [M] at the polymerization temperatures T ₁ and T ₂ .
Crystallization enthalpy (ΔH) and melting point (Tm) of copolymer
The product of and is the relational expression (ΔH) ^T1 · (Tm) ^T1 > (ΔH) ^T2 · (Tm) ^T2 [where (ΔH) ^T1 , (Tm) ^T1 , (ΔH) ^T2 and (Tm) ^T2 are Is the same meaning as. ], The polymerization conditions satisfying simultaneously are adopted. Where the polymerization temperatures T ₁ and T ₂
Specifically, the absolute value of the difference is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 15
Different temperature conditions above ℃. Regarding the temperatures of T ₁ and T ₂ , it suffices that the latter stage has excellent copolymerizability, and either one may have a higher temperature. The polymerization conditions are evaluated by using the metal compound (A) and aluminoxane and selecting the conditions excellent in copolymerizability.

(Method of verifying the relation of the above equation) The crystallization enthalpy (ΔH) is determined as follows. That is, a sheet that was hot pressed at a temperature of 190 ° C. was used as a sample, and a differential scanning calorimeter (manufactured by Perkin Elmer, DSC) was used.
7) is used and after melting at a temperature of 150 ° C. for 5 minutes,
The temperature is lowered to −50 ° C. at a rate of 10 ° C./min, and the crystallization enthalpy (ΔH) (unit: J / g) is calculated from the exothermic peak of crystallization observed in this process. Also, the melting point is
It is a value obtained from the temperature of the maximum peak position of the endothermic peak of melting when the temperature is further raised at a rate of 10 ° C / min. on the other hand,
The copolymerization conditions may be (1) normal pressure polymerization or pressure polymerization, (2) batch polymerization in which only ethylene is continuously supplied (however, the monomer conversion rate is 20% or less), or continuous polymerization ( 3) The initiation of the copolymerization reaction is carried out after the composition ratio of ethylene and the comonomer and the total concentration reach a steady state. (4) The molecular weight of the produced copolymer is not less than the critical molecular weight, and as the molecular weight increases, Polymerization should not be carried out in a region where the melting point rises. (5) Ethylene concentration and gaseous monomer concentration are calculated from the weight saturated and dissolved in the polymerization solvent used at a constant temperature. (6) In gas phase polymerization, The monomer charge composition ratio is calculated from the partial pressure or the monomer supply ratio. (7) Polymerization conditions in which the monomer composition in the system deviates due to the diffusion control of ethylene or a gaseous monomer are not possible. (8) Eth Not continue the polymerization in the absence consumption by emissions of polymerization, (9) the molar ratio of the catalyst components, the metal compound (A) / aluminoxane (B-2) = 1 / 100~
A range of 1/2000 is good, and so on.

Polymerization temperature T₂Ethylene produced in
Polymer (ΔH)^T2And melting point (Tm) ^T2Product of and monomer
The relationship with the charge composition ratio M is 0 ≦ (ΔH)^T2・ (Tm)^T2≤27,000-21600
[M]^0.56 Must be satisfied, and (ΔH)^T2And melting point (Tm)^T2When
When the product of is larger than this range, the metal compound (A) is preferable.
It does not show good copolymerizability. Note that this relationship is
Kuha 0 ≦ (ΔH)^T2・ (Tm)^T2≤27,000-22000
[M]^0.53 More preferably 0 ≦ (ΔH)^T2・ (Tm)^T2≤27,000-23000
[M]^0.53 More preferably 0 ≦ (ΔH)^T2・ (Tm)^T2≤27,000-24000
[M]^0.47 Even more preferably 0 ≦ (ΔH)^T2・ (Tm)^T2≤27,000-26000
[M]^0.40 Most preferably 0 ≦ (ΔH)^T2・ (Tm)^T2≤27,000-27,000
[M]^0.27 Is.

Preferred examples of the metal compound as the catalyst component (A) exhibiting such copolymerizability include the general formula CpM ¹ R ¹ _a R ² _b R ³ _c ... (I) (Cp-A _e − Cp) M ¹ R ¹ _a R ² _b (III) and

[0042]

[Chemical 5]

A compound represented by the formula (wherein Cp, A,
M ¹ , M ³ , X ² , Y ² , Z, R ^{1 to} R ³ , a, b,
c, e and w have the same meaning as described above. ), And among these, titanium compounds, zirconium compounds, hafnium compounds and vanadium compounds are more preferable.

In the present invention, in the presence of the above-mentioned polymerization catalyst, homopolymerization of ethylene or an ethylenic addition-polymerization monomer such as α-olefin having 3 to 20 carbon atoms, cyclic olefin, styrene and styrene derivative is selected. Copolymerization of ethylene with at least one selected. Examples of the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene 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 (XII)

[0045]

[Chemical 6]

(In the formula, R ^{16 to} R ²⁷ are each a hydrogen atom,
It represents a hydrocarbon group having 1 to 20 carbon atoms or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, which may be the same or different, and n represents an integer of 0 or more. ). The general formula (XI
Examples of the cyclic olefin represented by I) include norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 6-trimethylnorbornene; 5-phenylnorbornene; 5-benzylnorbornene; 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, 5,8,8a,
-Octahydronaphthalene; 2-isobutyl-1,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a, -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, 5,8,8a,-
Octahydronaphthalene; 2,3-dimethyl-1,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a, -octahydronaphthalene; 2-hexyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a, -octahydronaphthalene; 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a, -octahydronaphthalene; 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a, -octahydronaphthalene; 1,5
-Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a, -octahydronaphthalene and the like 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 the present invention, 2
A step polymerization method is adopted. In this case, except that the polymerization temperature of the first step is T ₁ and the polymerization temperature of the second step is T _2, and that at least ethylene or propylene monomer is present in the first step, the polymerization conditions are Can be set arbitrarily within the above range. That is, the composition charged with the monomer, the monomer species, the monomer concentration, and further the catalyst concentration and the polymerization time can be changed, and the desired ethylene polymer can be produced by these operations. Polymerization temperature T ₁
The proportion of the ethylene-based polymer produced in (1) is 0.05 to 90% by weight, preferably 0.07 to 90% by weight, more preferably
It is preferably in the range of 0.1 to 80% by weight. If this generation ratio is less than 0.05% by weight, non-Newtonian properties and properties as an elastomer are not fully exhibited, and 90% by weight
If it exceeds 0.1% by weight, the same as in the case of less than 0.05% by weight and the thermal stability of the produced polymer is deteriorated, which is not preferable.

Further, in the present invention, hydrogen treatment can be subsequently carried out after the completion of the polymerization reaction. This hydrogen treatment may be carried out by removing unreacted monomer or introducing hydrogen at atmospheric pressure to about 50 kg / cm ² G as it is. Other conditions are the same as in the case of polymerization. Thereby, the physical properties of the obtained polymer are essentially unchanged,
Thermal stability is improved by reducing unsaturated bonds. The ethylene polymer and the hydrogen-treated ethylene polymer of the present invention thus obtained have (a) a resin density of 0.86 to 0.97 g.
/ B) Differential scanning calorimeter (DS)
The maximum melting peak position that can be measured by C) is 50 to 2
In the range of 70 ° C., or substantially free of melting peaks, or exhibiting independent melting peaks,
(C) The intrinsic viscosity measured in decalin at a temperature of 135 ° C
0.01 to 20 deciliters / g, and (d) the 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 is 2.0. It is a polymer showing non-Newtonian property in the range of 40. 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 between the melt viscosity and 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.

Between the reduced viscosity η _{SP / c} (deciliter / g), the intrinsic viscosity [η] (deciliter / g), the Huggins constant k and the polymer concentration C (g / deciliter), the general formula (Huggins equation It is known that the relationship of η _{SP / c} = [η] + k [η] ² C is established. 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.

It has been shown in styrene / divinylbenzene copolymers that the introduction of branching into the polymer structure increases the Huggins constant [Journal of Polymer Sci., Vol. 9, Vol. , 265 (1952)]. LDPE with long chain branching
It is shown that the Huggins constant of linear and HDPE is large in LDPE [[Polymer Handbook (Polyme
r Handbook) "John Wiley Sons published (1975
Year)〕.

(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, LDPE shows a large Mw value with the same MI.

The ethylene polymer of the present invention can be used as a mixture with another thermoplastic resin. Examples of other thermoplastic resins include polyolefin-based resins, polystyrene-based resins, condensation-type high-molecular polymers, and addition-polymerization high-molecular polymers. Specific examples of the polyolefin resin include high-density polyethylene, low-density polyethylene, poly-3-methylbutene-1, poly-4-methylpentene-1, butene-1, and hexene- as comonomer components.
Linear low density polyethylene obtained by using 1, octene-1,4-methylpentene-1,3-methylbutene-1, etc., ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene -Acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene-based ionomers, polypropylene and the like.
Specific examples of the polystyrene-based resin include general-purpose polystyrene, isotactic polystyrene, and high-impact polystyrene (rubber-modified). Specific examples of the condensation type high molecular weight polymer include polyacetal resin, polycarbonate resin, polyamide resin such as nylon 6, nylon 6.6, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resin, polyimide resin, polysulfone resin. , Polyetherphone resin, polyphenylene sulfide resin, etc. Examples of the addition polymerization type high molecular weight polymer include, for example, a polymer obtained from a polar vinyl monomer and a polymer obtained from a diene monomer, specifically, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, acrylonitrile. Examples thereof include a butadiene-styrene copolymer, a diene polymer in which a diene chain is hydrogenated, and a thermoplastic elastomer. Among these thermoplastic resins, polyolefin resins are preferable.

[0055]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. 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) was added, and the reaction was carried out at 40 ° C. for 8 hours. afterwards,
Toluene was further 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. (2) Method for producing polyethylene In a pressure resistant autoclave equipped with a 1-liter stirring device, 400 ml of toluene and 10 mmol of methylaluminoxane prepared in the above (1) were added under a nitrogen atmosphere,
The temperature was raised to ° C. After saturated with ethylene partial pressure of 3 kg / cm ² G, 10 μmol of (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride was added to initiate polymerization.
The total pressure was kept constant and the reaction was carried out for 30 minutes. After completion of polymerization
The supply of ethylene was stopped, the mixture was cooled to 100 ° C. in about 60 seconds, and unreacted ethylene was removed by depressurization. Next, after thoroughly replacing the inside of the reaction system with nitrogen, further 85 ° C
Cooled down. 41 ml of a homogeneous solution was sampled from this reaction system, and polyethylene was recovered by reprecipitation with methanol. This is referred to as polymer [I]. Then, polymerization was further performed for 60 minutes while maintaining the ethylene partial pressure of 4 kg / cm ² G at 85 ° C. An increase in viscosity was observed in the reaction system while maintaining a uniform solution state. After completion of polymerization
Unreacted ethylene was removed in the same manner, thrown into a large amount of methanol, and polyethylene was recovered by filtration. The yield after drying was 19.8 g. This is referred to as a polymer [II]. Here, the production ratio of the polymer [I] and the polymer [II] was 0.376: 1 by weight. Further, when the amount of terminal vinyl groups was measured by the following method, it was 0.8 for the polymer [I].
78 carbons / 1000 carbons, polymer [II] 0.275 carbons / 1
It was 000 carbons. The reaction rate of vinyl groups of the polymer [I] obtained from the above results, that is, the polymer [I] incorporated into the polymer [II] by the copolymerization reaction was at least 17% or more. (Measurement of terminal vinyl group) A press sheet having a thickness of 100 µm was prepared and a transmission infrared absorption spectrum was measured. 90
Absorbance based on terminal vinyl groups near 7 cm ^-1 (A ₉₀₇ )
From the film thickness (t) and the resin density (D), the following equation n = 0.114A ₉₀₇ / [D · t] (where D: g / cm ³ , t: mm, n: carbon 100
It was determined by the number of vinyl groups per piece).

(3) Analysis of polymer [II] (a) Evaluation of thermal behavior Using a sheet obtained by hot pressing at 190 ° C. as a sample, measurement was carried out with 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 42.5 g / g. (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 0.947 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 3.7. (D) Measurement of intrinsic viscosity When the intrinsic viscosity in decalin at 135 ° C was determined, the intrinsic viscosity [η] was 2.05 deciliter / g.

Example 2 In Example 1- (2), (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
5 micromoles of ethylenebisindenyl zirconium dichloride was used instead of silane titanium dichloride, the polymerization time for obtaining the polymer [I] was 10 minutes, and the polymerization temperature for obtaining the polymer [II] was 90 ° C. It carried out similarly. As a result, the yield of polyethylene [II] was 29.
It was 8 g, and the production ratio of the polymer [I] and the polymer [II] was 0.202: 1 by weight. The analysis results are shown in Table 1. Example 3 In the polymerization reaction process for obtaining the polymer [II] of Example 2,
After adding 7.5 g of propylene, ethylene partial pressure 6 kg /
An ethylene-propylene copolymer was produced in the same manner with cm ² G. As a result, the polymer yield was 24.2 g,
The production ratio of the polymer [I] and the polymer [II] is 0 by weight.
It was 321: 1. The analysis results are shown in Table 1. After producing polyethylene [II] in the same manner as in Example 4 Example 2, after the unreacted ethylene was depressurization removed, was sufficiently replaced the inside of the reaction system further nitrogen, 90 ° C., a hydrogen partial pressure of 5 kg / cm ² G
Was reacted for 2 hours. Then, the reaction product was recovered in the same manner. The polyethylene yield was 29.0 g. A press sheet having a thickness of 0.3 mm was prepared and the infrared absorption spectrum was measured.
Absorption based on carbon-carbon double bonds, which was observable over cm ^-1, was not observed.

[0058]

[Table 1]

Note 1) In Example 1, the temperature was 85 ° C., 6
Polyethylene obtained only under 0 minute post-polymerization conditions

Evaluation of Polymer The non-Newtonian property was evaluated by determining the shear rate ω dependence of the melt viscosity η of the ethylene-based polymers obtained in Examples 1 and 2 and Comparative Example by the following method. As an apparatus, RMS E605 type manufactured by Rheometric Co. was used, and at 190 ° C., sinusoidal vibration was applied at a strain amount of 10% to measure the dynamic viscoelasticity. The results are shown in Fig. 1. Evaluation of copolymerizability (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (I) used in Example 1 and ethylenebisindenylzirconium dichloride (I) used in Example 2 II) ethylene and octene-1 were copolymerized under the conditions shown in Table 2 below, and the crystallization enthalpy (ΔH) and melting point (T
m) was measured. The results are shown in Table 2.

[0061]

[Table 2]

[0062]

[Table 3]

Note 1) MAO: methylaluminoxane prepared in Example 1- (1) 2) 400 ml of toluene and 3.50 at 25 ° C.
Calculated from the weight of ethylene dissolved in the mixed solvent of g of octene-1 at the polymerization temperature. 3) Tm: melting point, measured in the same manner as in Example 1- (3) 4) ΔH: enthalpy of crystallization, measured in the same manner as in Example 1- (3) 5) ΔH · Tm = 27000-21600 [M] Calculation from ^0.56 Note that the copolymerization method was specifically evaluated by the following apparatus and method. That is, the capacity of the polymerization reactor is 1.7
A pressure-resistant stainless steel autoclave of 6 liters and an inner diameter of 114 mm was used. This autoclave had anchor blades (thickness: 1.5 mm) as a stirrer, was 17 mm where the distance between the blade tip and the inner wall of the reactor was closest, and the area of one side of the blade was approximately 13 cm ² . . In the presence of a solvent,
In a stationary state, 70% or more of the blade area was fixed in a state of being immersed in a solvent before use. As an evaluation method, after thoroughly drying the above autoclave, 400 ml of dry toluene (water content: 5 ppm or less) (25 ppm) at room temperature under a nitrogen atmosphere
Then, octene-1 (water content: 5 ppm or less) was added in a specified amount by weight. Further, an organometallic compound (eg, aluminoxane, alkylaluminum, etc.) was added as a catalyst component. Then, it stirred at room temperature for 3 minutes. Further, thereafter, the temperature was raised to the polymerization temperature in a sealed state, and after the pressure reached a certain level, ethylene was introduced. Further, the supply of ethylene was stopped, and the saturated state was confirmed by the fact that there was no pressure drop. The stirring speed at this time was kept constant at 500 rpm. The initiation of copolymerization was performed by injecting another catalyst component while maintaining this state.

After the initiation of the copolymerization, it is necessary that the ethylene flow rate is controlled at a normal pressure of not more than 3 normal liters / minute and the temperature control range is at the polymerization set temperature ± 2 ° C. If control is not performed in such a state, it is necessary to re-evaluate by changing the catalyst amount. After carrying out the copolymerization for a certain period of time, the supply of ethylene was stopped, and unreacted ethylene was immediately removed by depressurization, followed by deactivation with methanol. The total amount of the solvent in the catalyst component was adjusted to 1% or less with respect to the total volume of the polymerization solvent toluene and octene-1.

[0065]

According to the present invention, the non-Newtonian property is improved, good film moldability and blow moldability are imparted, the energy and cost of molding process are reduced, and the high speed moldability is achieved. It is possible to highly efficiently obtain an ethylene-based polymer to which is added or an ethylene-based polymer having preferable properties as an elastomer.

[Brief description of drawings]

FIG. 1 is a graph showing the shear rate dependence of the melt viscosity of the ethylene polymers obtained in Examples 1 and 2 and Comparative Example.

─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-5-320248 (JP, A) JP-A-5-331232 (JP, A) JP-A-3-210307 (JP, A) JP-A-3- 234717 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 10/02 C08F 4/64-4/658

Claims (5)

(57) [Claims] 1. A having a terminal vinyl group-forming ability (A) below
Ethylene compound by a multi-stage polymerization method using a catalyst containing as a main component a metal compound selected from the general formulas (III) and (VI) and (B) a compound capable of forming an ionic complex from the metal compound or a derivative thereof. In producing a polymer or a copolymer of ethylene and an ethylenic addition-polymerized monomer,
(1) Copolymerization ethylene / octene-1 molar ratio [octene-1 / (ethylene + octene-1)] M produced at the polymerization temperatures T ₁ and T ₂ The product of the melting point (Tm) of the polymer and the enthalpy of crystallization (ΔH) is the formula (Tm) ^T1 · (ΔH) ^T1 > (Tm) ^T2 · (ΔH)
^T2 [where (Tm) ^T1 and (ΔH) ^T1 represent the melting point and enthalpy of crystallization of the ethylene / octene-1 copolymer synthesized at the polymerization temperature T ₁ , respectively, and (Tm) ^T2 and (ΔH) ^T2 represent respectively The melting point and enthalpy of crystallization of an ethylene / octene-1 copolymer synthesized at a polymerization temperature T ₂ are shown. ], And (2) above (1)
In, the product of the melting point (Tm) ^{T2 of} the ethylene / octene-1 copolymer synthesized at the polymerization temperature T ₂ and the enthalpy of crystallization (ΔH) ^T2 is expressed by the formula 0 ≦ (Tm) ^T2 · (ΔH) ^T2 ≦ 27,000. -216
Polymerization temperature conditions and catalysts that simultaneously satisfy the relationship of 00 [M] ^0.56 are adopted, the polymerization temperature of the first stage is T _1, and the polymerization temperature of the second stage is T _2. Of producing a base polymer. ^{_{(Cp-A e -Cp) M}} 1 R 1 a R 2 b ··· (III) wherein, ^{M 1} is titanium, zirconium or hafnium source
Cp is a cyclopentadienyl group, substituted cyclo
Pentadienyl group, indenyl group, substituted indenyl group,
Tetrahydroindenyl group, substituted tetrahydroindenyl
Group, fluorenyl group or substituted fluorenyl group.
R ¹ and R ² are each independently a hydrogen atom, an oxygen atom,
Rogen atom, C1-C20 alkyl group, C1-C1
An alkoxy group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Rukyryl group or arylalkyl group, carbon number
1 to 20 acyloxy group, allyl group, substituted allyl group,
Substituents containing silicic atom, an acetyl acetonate group, or
A substituted acetylacetonate group is shown. A is methylene, di
Methylmethylene, ethylene, cyclohexylene, dimethy
Lucillene, dimethylgermylene or dimethylstanile
Indicate the a and b are each an integer of 0 to 2
, A + b represents the valence of M ¹ of −2, and e is an integer of 0 to 6.
Indicates a number. ] [Chemical 1] [ Wherein M ³ is titanium, zirconium or hafnium raw material]
Cp is a cyclopentadienyl group, substituted cyclo
Pentadienyl group, indenyl group, substituted indenyl group,
Tetrahydroindenyl group, substituted tetrahydroindenyl
Group, fluorenyl group or substituted fluorenyl group.
X ² is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
Kill group, aryl group having 6 to 20 carbon atoms, alkyl aryl
Group or arylalkyl group or having 1 to 20 carbon atoms
Indicates an alkoxy group. Z is SiR ⁷ ₂ , CR ⁷ ₂ , Si
R ⁷ ₂ SiR ⁷ ₂ , CR ⁷ ₂ CR ⁷ ₂ , CR ⁷ ₂ CR ⁷
₂ CR ⁷ ₂ , CR ⁷ = CR ⁷ , CR ⁷ ₂ SiR ⁷ ₂ or
Indicates GeR ^{7 _2, Y} ₂ is ^{-N (R 8) -, -} O -, -
S- or -P ^{(R 8)} - indicates a. R ⁷ is a hydrogen atom or
Is alkyl, aryl having up to 20 non-hydrogen atoms,
Silyl, halogenated alkyl, halogenated aryl groups
R ⁸ is a group selected from
An alkyl group having 1 to 10 or an aryl group having 6 to 10 carbon atoms
is there. w represents 1 or 2. ] 2. The method for producing an ethylene polymer according to claim 1, wherein the ratio of the amount of the ethylene polymer produced in the first stage is 0.05 to 90% by weight. 3. In the first-stage and second-stage polymerization reactions,
The method for producing an ethylene-based polymer according to claim 1 or 2, wherein the ethylenic addition-polymerized monomer is not introduced into at least one reaction system. 4. The method for producing an ethylene-based polymer according to claim 1, wherein ethylene is not used in the second-stage polymerization reaction. 5. The method for producing an ethylene polymer according to claim 1, wherein hydrogen treatment is carried out subsequently to the polymerization reaction.