JPH11335419A - Ethylene-based copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene-based copolymer useful as a macromonomer for producing syndiotactic polystyrene graft copolymers excellent in heat resistance, chemical resistance and improved in tenacity, elongation and rigidity, etc., and a material for obtaining a compatibilizer in compositions of various polystyrenes and rubber components. SOLUTION: This ethylene-based copolymer is a copolymer comprising ethylene (A), a 3-20C α-olefin (B), a diene-based monomer having a styrene-based vinyl group or a diene-based monomer having a conjugated ene (C) and, if needed, an aromatic vinyl monomer (D) and a molar ratio of A/B is 20/80-97/3, C is 0.001-20 mole % and D is 0.01-30 mole %, and has vinyl groups derived from the diene-based monomer in a molecular chain having 0.1-80% rate of partial crosslinks K expressed by the following equation: K=(1-U/V)×100% (U is the amount of unreacted vinyl group units in the diene-based monomer in the polymer and V is the amount of the repeating unit derived from the diene-based monomer in the polymer).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene copolymer and a method for producing the same, and more particularly, to a novel ethylene copolymer having a vinyl group in a molecular chain of the ethylene copolymer and an efficient ethylene copolymer. Manufacturing method.

[0002]

2. Description of the Related Art A styrenic polymer having a high syndiotacticity has been developed (JP-A-62-104818).
This polymer is excellent in heat resistance, chemical resistance, etc., but has insufficient toughness and elongation, poor compatibility with other resins, and limited applications. I couldn't escape being done.

[0003] In order to solve such a drawback, it has been proposed to impart toughness to the styrenic polymer having the above syndiotactic structure by copolymerizing styrene and olefins (Japanese Patent Laid-Open No. Hei 3 (1991) -1991). 7705, 4-130114, 4-300904). However, also in these, toughness and elongation,
Furthermore, improvement in compatibility with other resins is not always sufficient, and heat resistance may decrease,
There has been a demand for a technique capable of further improving toughness and the like while maintaining good heat resistance.

[0004] Therefore, an ethylene / α-olefin / diene copolymer is produced using a Ziegler-Natta catalyst or a supported catalyst system, and a styrene having a syndiotactic structure in the reactive vinyl group of the polymer. There has been proposed a method for improving toughness by grafting a polymer (Japanese Patent Laid-Open No. Hei.
247147). According to this method, although the toughness of the syndiotactic polystyrene-based polymer is improved, elongation, rigidity and low-temperature impact resistance are not sufficient, and improvement has been desired.

In these catalyst systems, ethylene and α
-Since the copolymerizability of the olefin is low and the activity is low, it is not easy to control the composition of the copolymer and the crosslinked structure, and an efficient production method has been desired.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an ethylene which is extremely useful as a macromonomer for obtaining a resin having excellent elongation, rigidity and low-temperature impact resistance and excellent compatibility with other resins. An object of the present invention is to provide a system copolymer and an efficient production method thereof. Furthermore, it is used as a macromonomer to obtain a syndiotactic polystyrene graft copolymer having excellent heat resistance, chemical resistance, and toughness, elongation and rigidity, and a composition of syndiotactic polystyrene and a rubber component. It is an object of the present invention to provide an ethylene copolymer which is extremely useful as a material for obtaining a compatibilizer in a product or a general composition of a polystyrene and a rubber component, and an efficient production method thereof.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a styrene vinyl group crosslinked in the molecular chain of an ethylene copolymer and an uncrosslinked styrene group. Both of the vinyl groups are introduced at a certain ratio, and the polystyrene graft copolymer obtained by graft-polymerizing styrene to an uncrosslinked styrene vinyl group is elongated, and has excellent rigidity and low-temperature impact resistance, The present inventors have found that the polystyrene graft copolymer has excellent compatibility with other resins, and have completed the present invention based on this finding.

That is, the present invention provides the following. (1) Ethylene (A), at least one of 3 to 3 carbon atoms
0-olefin (B) and a diene monomer having at least one styrene vinyl group or a diene monomer (C) having at least one conjugated ene, wherein ethylene (A) / The molar ratio of the α-olefin (B) is 20/80 to 97/3, and the repeating unit derived from the component (A), the KARA diene-based monomer (C), is 0.001 to 20 mol%. Is 100 mol%, and the ratio K of the partial crosslink derived from the diene monomer represented by the following formula (1) is 0.1 to 80%. An ethylene copolymer having a vinyl group.

[0009]

(Equation 2)

(2) Ethylene (A), at least one α-olefin having 3 to 30 carbon atoms (B), at least 1
A copolymer of a diene monomer having at least one styrene-based vinyl group or a diene monomer having at least one conjugated ene (C) and at least one aromatic vinyl monomer (D), wherein ethylene (A) / Α-olefin (B) molar ratio of 20/80 to 97/3,
When the repeating unit derived from the diene monomer (C) is 0.0
1 to 20 mol%, the repeating unit derived from the aromatic vinyl monomer (D) is 0.01 to 30 mol%, and the total amount of these components is 100 mol%. Of partial crosslinks derived from diene-based monomers
Is an ethylene-based copolymer having a vinyl group derived from a diene-based monomer in a molecular chain of 0.1 to 80%. (3) The ethylene copolymer according to (1) or (2), wherein the α-olefin having 3 to 30 carbon atoms (B) is propylene. (4) The ethylene copolymer according to any one of (1) to (3), wherein the vinyl group derived from the diene monomer is a styrene vinyl group. (5) (a) transition metal compound, (b) (a) general formula (2)

[0011]

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(Wherein R ^{1 to} R ⁵ each have 1 to 1 carbon atoms)
8 represents an alkyl group, which may be the same or different; Y ^{1 to} Y ³ each represent a Group 13 element of the periodic table; they may be the same or different; Represents a number from 0 to 50, respectively, and a +
b is 1 or more. ) And / or general formula (3)

[0013]

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Wherein R ⁶ and R ⁷ each have 1 carbon atom
To 8 alkyl groups, which may be the same or different, and Y ⁴ and Y ⁵ each represent
Represents a group 3 element, which may be the same or different, c and d each represent a number of 0 to 50,
c + d is 1 or more. An oxygen-containing compound represented by
And / or (ii) each monomer is copolymerized using a catalyst formed using a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (a). The method for producing an ethylene-based copolymer according to any one of (1) to (4). (6) The method for producing an ethylene copolymer according to (5), wherein (a) the transition metal compound is represented by the following general formula (4).

[0015]

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[Wherein M¹Is group 3 to 10 of the periodic table or la
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, fluorenyl group, substituted fluorenyl group,
Hexahydroazulenyl group, substituted hexahydroazuleni
Group, tetrahydroindenyl group, substituted tetrahydroyl
Ndenyl group, tetrahydrofluorenyl group, substituted tetra
Hydrofluorenyl group, octahydrofluorenyl group,
Substituted octahydrofluorenyl group, heterocyclopenta
Dienyl group, substituted heterocyclopentadienyl group,
Group, phosphide group, hydrocarbon group and silicon-containing group
A ligand selected from the group consisting of A¹And A^TwoCross-linked through
Structures, and they are identical or different.
May be X¹Represents a σ-binding ligand, and X
¹If there are multiple Xs¹Are the same but different
Well, other X¹, E¹, E^TwoOr Y⁶Cross-linked with
Is also good. Y⁶Represents a Lewis base;⁶Where there are multiple
If multiple Y⁶May be the same or different, and the other Y
⁶, E¹, E^TwoOr X¹May be cross-linked with A¹Passing
And A^TwoIs a frame composed of hydrocarbon groups having 1 or more carbon atoms.
Bridging groups, which may be the same or different
Good. q is an integer of 1 to 5 [(M¹Valence) -2)
And r represents an integer of 0 to 3. The transition metal represented by
Compound. (7) (a) The transition metal compound is represented by the following general formula (5).
Etch described in (5), characterized in that
A method for producing a len-based copolymer.

[0017]

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(Wherein, E ³ and E ⁴ represent an unsubstituted or substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulle group group, tetrahydroindenyl group, substituted tetrahydroindenyl groups, tetrahydrofluorenyl groups, substituted tetrahydrofluorenyl group, octahydrofluorenyl group, a substituted octahydrofluorenyl group, a ³ and a
⁴ is selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group or a halogenated aryl group, or oxygen, nitrogen, sulfur or silicon. A hydrocarbon group having 1 to 20 carbon atoms containing a hetero atom,
Is a hydrocarbon group having 2 to 10 carbon atoms linking E ³ and E ⁴ , or a carbon group having 1 to 3 carbon atoms including silicon, germanium or tin.
A hydrocarbon group of 10 or a carbon, silicon, germanium or tin atom, and A ³ and A ⁴ may be connected to each other to form a ring structure among A ³ , A ⁴ and Q . R ⁸ and R ⁹ is a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, silicon-containing alkyl group, or each aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, and M ² Is titanium, zirconium or hafnium. (8) The method for producing an ethylene-based copolymer according to (5), wherein (a) the transition metal compound is represented by the following general formula (6).

[0019]

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(Where M^TwoIs titanium, zirconium or
Hafnium, Cp^*Is M^TwoTo η^FiveTied in a join style
Combined cyclopentadienyl group, substituted cyclopentadiene
Nil or indenyl group, substituted indenyl group, fluor
Nyl group, substituted fluorenyl group, hexahydroazulenyl
Group, substituted hexahydroazulenyl group, tetrahydroin
Denenyl group, substituted tetrahydroindenyl group, tetrahydrid
Rofluorenyl group, substituted tetrahydrofluorenyl group,
Octahydrofluorenyl group, substituted octahydrofluor
A enyl group. X¹Represents a σ ligand, and n is 1 or 2
And multiple X ¹Even if they are the same or different
And may be bonded via any group. Y
⁷Is O, S, NR, PR or CR_TwoOr O
R, SR, NR_TwoOr PR_TwoNeutral two electricity selected from
Z is a SiR_Two, CR_Two, Si
R_TwoSiR_Two, CR_TwoCR_Two, CR = CR, CRSiR
_Two, GeR_Two, BR, BR_TwoWhere R
Represents, in each case, hydrogen, an alkyl group, an aryl group,
Ryl group, alkyl halide, aryl halide, and
And a combination of at least two of these
Selected from the group consisting of the following non-hydrogen atoms
It is. Further, two or more of the R groups may be Z,
Is Y⁷And Z may form a fused ring system
No. )

[0021]

Embodiments of the present invention will be described below. 1. Ethylene-based copolymer The ethylene-based copolymer according to the present invention comprises ethylene (A), at least one α-olefin having 3 to 30 carbon atoms (B), and at least one diene-based styrene-based vinyl group. Monomer or diene-based monomer (C) having at least one conjugated ene, and at least one aromatic vinyl monomer (D) optionally used
Wherein the molar ratio of ethylene (A) / α-olefin (B) is from 20/80 to 97/3, and the repeating unit derived from the diene monomer (C) is from 0.001 to 2
0 mol%, if necessary, the repeating unit derived from the aromatic vinyl monomer (D) is 0.01 to 30 mol%, the total amount of these components is 100 mol%, and the following (1) An ethylene copolymer having a vinyl group derived from a diene monomer in a molecular chain in which the ratio K of partial crosslinking derived from the diene monomer represented by the formula is 0.1 to 80%.

[0022]

(Equation 3)

(1) Monomer The ethylene copolymer according to the present invention is obtained by copolymerizing the following monomers. (A) Ethylene (A) Any type may be used, in which hydrogen is replaced by halogen or the like. (B) α-olefin (B) α-olefin monomer excluding ethylene. Specifically, propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; decene-1; 4-phenylbutene-1; 6-phenylhexene-1; -Methylbutene-1; 4-methylpentene-1; 3-methylpentene-1; 3-methylhexene-
1; 4-methylhexene-1; 5-methylhexene-
1, 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; α-olefin such as vinylcyclohexane, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; 1,3-difluoroethylene; 3-fluoropropene; trifluoroethylene;
Halogen substituted α-olefins such as 3,4-dichlorobutene-1, cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; Cyclic olefins such as -methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; and 5-benzylnorbornene, and one or more of these are used. (C) Diene monomer (C) The diene monomer (C) used in the present invention is a diene monomer having styrene vinyl or a diene monomer having conjugated ene.

The diene monomer having a styrene vinyl is a diene monomer having a vinyl group bonded to a phenyl group, and is a vinylstyrene compound represented by the following general formulas (7) and (8).

[0025]

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[0026]

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(Wherein X ² represents an aromatic compound residue such as benzene, naphthalene, anthracene, etc .; an aromatic compound residue substituted with an alkyl group having 1 to 20 carbon atoms, such as toluene, xylene, ethylbenzene, etc.); , A halogen-substituted aromatic compound residue such as bromobenzene,
Y ⁸ represents CH ₂ , an alkylene group, an alkylidene group,
n represents 0 or an integer of 1 to 20. Specifically, as the compound represented by the general formula (7),
o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, (o-, m-, p-) divinyltoluene, (o-, m-, p-) 2-propenylstyrene,
(O-, m-, p-) 3-butenylstyrene, (o-,
m-, p-) 4-Pentenylstyrene and the like, and examples of the compound represented by the general formula (8) include the following compounds.

[0028]

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The diene monomer having a conjugated ene is a monomer having at least two continuous carbon-carbon double bonds in the molecule and having 4 to 20 carbon atoms. Examples of the conjugated diene compound having 4 to 20 carbon atoms include butadiene, isoprene, chloroprene,
1,3-hexadiene, 1,3,5-hexatriene,
Examples thereof include 1,3-heptadiene and 1,3,6-heptatriene. (D) Aromatic vinyl monomer (D) The aromatic vinyl monomer (D) used in the present invention is a compound represented by the general formula (9).

[0030]

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Wherein X ³ represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; n represents an integer of 1 to 5, and when n is 2 or more, each X ³ may be the same or different. ] Is used. Specifically, styrene, p-methylstyrene, m-methylstyrene, o
-Methylstyrene, 2,4-dimethylstyrene, 2,5
-Dimethylstyrene, 3,4-dimethylstyrene, 3
Alkyl styrenes such as 5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene and p-tert-butylstyrene; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene , O-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene,
halogenated styrenes such as o-methyl-p-fluorostyrene, alkoxystyrenes such as methoxystyrene, ethoxystyrene and t-butoxystyrene, vinylbiphenyls, vinylphenylnaphthalenes, vinylphenylanthracenes, halogenated vinylbiphenyls, Alkyl silyl vinyl biphenyls, halogen-substituted alkyl styrene, alkyl silyl styrenes, phenyl group-containing silyl styrenes, halogen-containing silyl styrenes,
Silyl group-containing silyl styrenes, or a mixture of two or more of these. Further, vinyl naphthalenes and vinyl anthracenes, and substituted products thereof can also be used. (2) Composition The ethylene-based copolymer of the present invention has the above-mentioned composition. Ratio
It is preferably in the range of 25/75 to 93/7. More preferably, it is 30/70 to 90/10. (A) Ethylene (A) unit Ethylene (A) unit needs to be 20 to 97 mol% based on the total amount of α-olefin (B). Preferably, it is 25 to 93 mol%. More preferably, it is 30 to 90 mol%. If the amount is less than 20 mol%, the brittleness of the ethylene-based copolymer increases, which is not preferable. On the other hand, if it exceeds 97 mol%, the crystallinity is increased and the physical properties such as solubility are undesirably reduced. (B) α-Olefin (B) unit The α-olefin (B) unit needs to be 3 to 80 mol% with respect to the total amount of ethylene (A). Preferably, it is 7 to 75 mol%. More preferably,
10 to 70 mol%. When the amount is less than 3 mol%, the crystallinity of the ethylene copolymer becomes high, which is not preferable. On the other hand, if it exceeds 80 mol%, the brittleness increases, which is not preferable. (C) Unit of diene monomer (C) The unit of diene monomer (C) is 0.00 relative to all components.
It needs to be 1 to 20 mol%. Preferably,
0.005 to 15 mol%. More preferably, 0.0
1 to 10 mol%. If it is less than 0.001 mol%, the rigidity is undesirably reduced. On the other hand, if it exceeds 20 mol%, the crosslinking reaction takes place too much and the physical properties deteriorate, which is not preferred. (D) Aromatic vinyl monomer (D) unit When an aromatic vinyl monomer (D) unit is introduced into the ethylene copolymer of the present invention, it is required to be 0.01% based on all components.
〜30 mol% is required. If it is less than 0.01%, the compatibility with the styrenic polymer is lowered, which is not preferable. If it exceeds 30 mol%, the brittleness increases, which is not preferable. (3) Positional relation of vinyl group The positional relation of the styrene-based vinyl group or the olefin-based vinyl group in the ethylene-based copolymer of the present invention may be any structure that is adjacent to or separated from the main chain structure. May be. (4) Crosslinked Structure In the ethylene copolymer of the present invention, a vinyl group derived from the diene monomer partially reacts to form a crosslinked structure. The cross-linked structure may be one that has reacted and bonded between molecular chains, or one that has reacted and bonded within a molecular chain. The progress of crosslinking can be controlled by the type of diene monomer or the type of catalyst used. (5) Ratio K of Partial Crosslinking The ratio K of partial crosslinking is determined by the above formula (1)
As the unit amount in the formula (1), a value obtained by ¹ H-NMR, infrared absorption analysis or the like can be used.

K needs to be 0.1-80%. Preferably, it is 0.5 to 60%. More preferably, it is 1.0 to 50%. If K is less than 0.1%, the rigidity does not appear because the crosslinking ratio is too low. On the other hand, if it exceeds 80%, crosslinking is excessive and gelation occurs, which is not preferable. (6) Intrinsic viscosity [η] measured in decalin at 135 ° C. The ethylene copolymer of the present invention preferably has an [η] of 0.01 to 15 deciliter / g. More preferably,
0.05 to 12 deciliter / g, more preferably 0.1 to 12 deciliter / g
10 deciliters / g. If it is less than 0.01 deciliter / g, the compatibilizing ability when grafted may be reduced. If it exceeds 15 deciliters / g, the solubility in a solvent at the time of graft polymerization may decrease. (7) Molecular weight distribution (Mw / Mn) measured by GPC Mw / Mn of the ethylene copolymer of the present invention is preferably 25 or less. More preferably, it is 10 or less. More preferably, it is 5 or less. When Mw / Mn exceeds 25, the grafting ratio during graft polymerization decreases, and the physical properties of the obtained graft polymer may decrease. (8) Crystallinity The ethylene copolymer of the present invention is preferably amorphous. It may have a melting point. 2. Method for Producing Ethylene-Based Copolymer The ethylene-based copolymer of the present invention comprises (a) a transition metal compound, (b) (a) an oxygen-containing compound, and / or (b) a transition metal compound of the component (a). The compound can be produced by copolymerization using a compound capable of forming an ionic complex by reacting with the compound and, if necessary, a catalyst comprising (c) an alkylating agent. (1) Each component of the catalyst (a) Transition metal compound As the transition metal compound (a), various compounds can be used, but usually, the following compounds are preferably used. (I) a compound represented by the following general formula (4)

[0033]

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[Wherein, M¹Is group 3 to 10 of the periodic table or la
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, fluorenyl group, substituted fluorenyl group,
Hexahydroazulenyl group, substituted hexahydroazuleni
Group, tetrahydroindenyl group, substituted tetrahydroyl
Ndenyl group, tetrahydrofluorenyl group, substituted tetra
Hydrofluorenyl group, octahydrofluorenyl group,
Substituted octahydrofluorenyl group, heterocyclopenta
Dienyl group, substituted heterocyclopentadienyl group,
Group, phosphide group, hydrocarbon group and silicon-containing group
A ligand selected from the group consisting of A¹And A^TwoCross-linked through
Structures, and they are identical or different.
May be X¹Represents a σ-binding ligand, and X
¹If there are multiple Xs¹Are the same but different
Well, other X¹, E¹, E^TwoOr Y⁶Cross-linked with
Is also good. Y⁶Represents a Lewis base;⁶Where there are multiple
If multiple Y⁶May be the same or different, and the other Y
⁶, E¹, E^TwoOr X¹May be cross-linked with A¹Passing
And A^TwoIs a frame composed of hydrocarbon groups having 1 or more carbon atoms.
Bridging groups, which may be the same or different
Good. q is an integer of 1 to 5 [(M¹Valence) -2)
And r represents an integer of 0 to 3. ] X above¹As a specific example, a halogen atom, a carbon number 1
To 20 hydrocarbon groups, an alkoxy group having 1 to 20 carbon atoms,
Aryloxy group having 6 to 20 carbon atoms, 1 to 20 carbon atoms
Amide group, silicon-containing group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 phosphide group, sulfide group having 1 to 20 carbon atoms, charcoal
An acyl group having a prime number of 1 to 20 is exemplified. Also,
Of Y⁶Specific examples of amines, ethers, phos
Examples include fins and thioethers.
In addition, A¹And A^TwoAs a specific example, for example,
General formula

[0035]

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(T ¹ and T ² are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and may be bonded to each other to form a ring. And e is an integer of 1 to 4. Specific examples thereof include a methylene group,
Examples thereof include an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, a 1,2-cyclohexylene group, and a vinylidene group (CH 2 ＝ C な ど). Among these, a methylene group, an ethylene group and an isopropylidene group are preferred.

Specific examples of the transition metal compound represented by the general formula (4) of the present invention include (1,1′-ethylene)
(2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene)-
Bis (indenyl) zirconium dichloride, (1,
2′-methylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, 2'-
Isopropylidene) (2,1′-isopropylidene)-
Bis (indenyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-ethylene) -bis (3-
Methylindenyl) zirconium dichloride, (1,
2'-ethylene) (2,1'-ethylene) -bis (3-
Methylindenyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-ethylene) -bis (4
5-benzoindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene)-
Bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2 2'-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1 '
-Ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-ethylene) (2
2′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, ( 1,
1′-ethylene) (2,2′-ethylene) -bis (4-
Phenylindenyl) zirconium dichloride, (1,
2'-ethylene) (2,1'-ethylene) -bis (4-
Phenylindenyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-ethylene) -bis (3-
Methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,1′-ethylene )
(2,2′-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-benzoindenyl) zirconium Dichloride, (1,1′-ethylene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) -bis (indenyl) zirconium Dichloride, (1,1′-isopropylidene) (2,2′-ethylene) -bis (indenyl)
Zirconium dichloride, (1,2'-methylene)
(2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-
Ethylene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-methylene)-
Bis (indenyl) zirconium dichloride, (1,
1′-methylene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2 ′
-Methylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1'-
Isopropylidene) (2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene) (3-methylcyclopentadienyl) (cyclopentadienyl) Zirconium dichloride, (1,1′-isopropylidene) (2,2 ′
-Isopropylidene) (3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-propylidene) (2,2′-propylidene) (3-methylcyclopentadienyl) (cyclopentane Dienyl) zirconium dichloride, (1,1'-
Ethylene) (2,2′-methylene) -bis (3-methylcyclopentadienyl) zirconium dichloride,
(1,1′-methylene) (2,2′-ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-
Ethylene) -bis (3-methylcyclopentadienyl)
Zirconium dichloride, (1,1'-ethylene)
(2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,
1′-methylene) (2,2′-methylene) -bis (3-
Methylcyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene)
(2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-methylene) -bis (3
4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′- Methylene) (2,2′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,1′-methylene) (2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (3,4-
Dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene)-
Bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′- Methylene)
(2,1′-methylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (3-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,
2'-ethylene) (2,1'-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-
Methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (3,4-
Dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride and the like, and zirconium in these compounds There can be mentioned those substituted with titanium or hafnium. Of course, it is not limited to these. Further, a similar compound of a metal element of another group or a lanthanoid series may be used. (Ii) a compound represented by the following general formula (5) or (10)

[0038]

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[0039]

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(In the above equations (5) and (10),
E ³ and E ⁴ represent an unsubstituted or substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group,
Substituted hexahydroisochromeno Azure group, tetrahydroindenyl group, substituted tetrahydroindenyl groups, tetrahydrofluorenyl groups, substituted tetrahydrofluorenyl group, octahydrofluorenyl group, a substituted octahydrofluorenyl group, A ³ And A ⁴ are a hydrogen atom, a carbon number of 1 to 1
0 alkyl group, or aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group or aryl halide group, or 1 to 20 carbon atoms containing a heteroatom selected from oxygen, nitrogen, sulfur or silicon. Q is a hydrocarbon group having 2 to 10 carbon atoms linking E ³ and E ⁴ or a hydrocarbon group having 1 to 10 carbon atoms including silicon, germanium or tin, or carbon, silicon, germanium Or a tin atom, and A ³
And A ⁴ may be linked to each other to form a ring structure among A ³ , A ⁴ and Q. R ⁸ and R ⁹ are a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a silicon-containing alkyl group, an aryl group having 6 to 20 carbon atoms,
An alkylaryl group or an arylalkyl group, and M ² is titanium, zirconium or hafnium. In the above, specific examples of E ³ and E ⁴ include a cyclopentadienyl group, a methylcyclopentadienyl group,
Dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, indenyl group, 3-methylindenyl group, tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, hexahydroazulenyl group, octahydrofluorenyl And a 2,7-di-t-butylfluorenyl group.

As A ³ and A ⁴ , specifically,
Examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenyl group, a toluyl group, a fluorophenyl group, a methoxyphenyl group, and a benzyl group. Furthermore, A
^{If 3} and A ⁴ are not linked to each other to form a ring structure between the A ^3, A ⁴ and Q, A ^3, Examples of the group A ⁴ and Q forms, cyclopentylidene group, cyclohexylidene And a tetrahydropyran-4-ylidene group.

Preferred examples of R ⁸ and R ⁹ include:
Examples include a chlorine atom, a methyl group, a phenyl group, and a trimethylsilylmethyl group. As the above transition metal compound, specifically, ethylene bis (1-indenyl)
Zirconium dichloride, ethylenebis (tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadiyl) Enil)
(Fluorenyl) zirconium dichloride, isopropylidene (9-fluorenyl) (1-indenyl) zirconium dichloride, dimethylsilyl-bis- (2-methylindenyl) zirconium dichloride, dimethylsilyl-bis- (2-methylbenzoindenyl) zirconium Dichloride, dimethylsilyl-bis- (2-methyl-
4-phenylindenyl) zirconium dichloride, dimethylsilyl-bis- (2-methyl-4-naphthylindenyl) zirconium dichloride, and the like. (Iii) a compound represented by the following general formula (6)

[0043]

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(Where M^TwoIs titanium, zirconium or
Hafnium, Cp^*Is M^TwoTo η^FiveTied in a join style
Combined cyclopentadienyl group, substituted cyclopentadiene
Nil or indenyl group, substituted indenyl group, fluor
Nyl group, substituted fluorenyl group, hexahydroazulenyl
Group, substituted hexahydroazulenyl group, tetrahydroin
Denenyl group, substituted tetrahydroindenyl group, tetrahydrid
Rofluorenyl group, substituted tetrahydrofluorenyl group,
Octahydrofluorenyl group, substituted octahydrofluor
A enyl group. X¹Represents a σ ligand, and n is 1 or 2
And multiple X ¹Even if they are the same or different
And may be bonded via any group. Y
⁷Is O, S, NR, PR or CR_TwoOr O
R, SR, NR_TwoOr PR_TwoNeutral two electricity selected from
Z is a SiR_Two, CR_Two, Si
R_TwoSiR_Two, CR_TwoCR_Two, CR = CR, CRSiR
_Two, GeR_Two, BR, BR_TwoWhere R
Represents, in each case, hydrogen, an alkyl group, an aryl group,
Ryl group, alkyl halide, aryl halide, and
And a combination of at least two of these
Selected from the group consisting of the following non-hydrogen atoms
It is. Further, two or more of the R groups may be Z,
Is Y⁷And Z may form a fused ring system
No. Here, the substituted cyclopentadienyl group is, for example,
For example, a group substituted by one or more alkyl groups having 1 to 6 carbon atoms
Clopentadienyl group, specifically, methylcyclopen
Tadienyl group; 1,2-dimethylcyclopentadienyl
A group; a 1,2,4-trimethylcyclopentadienyl group;
1,2,3,4-tetramethylcyclopentadienyl
Group; trimethylsilylcyclopentadienyl group; 1,3
A di (trimethylsilyl) cyclopentadienyl group;
Tert-butylcyclopentadienyl group; 1,3-di
(Tert-butyl) cyclopentadienyl group; carbon
A hydrocarbyl group of formulas 1 to 20, halohydrocarb
And the like. Further, a substituted indenyl group is, for example,
Tilindenyl group, dimethylindenyl group, tetramethyl
A ruindenyl group and a hexamethylindenyl group.
As the substituted tetrahydroindenyl group, for example, 4,
5,6,7-tetrahydroindenyl group; 1-methyl-
4,5,6,7-tetrahydroindenyl group; 2-methyl
1,4,5,6,7-tetrahydroindenyl group;
2-dimethyl-4,5,6,7-tetrahydroindeni
1,3-dimethyl-4,5,6,7-tetrahydryl
Loindenyl group; 1,2,3-trimethyl-4,5
6,7-tetrahydroindenyl group; 1,2,3,4
5,6,7-heptamethyl-4,5,6,7-tetrahi
Droindenyl group; 1,2,4,5,6,7-hexame
A tyl-4,5,6,7-tetrahydroindenyl group;
1,3,4,5,6,7-hexamethyl-4,5,6
7-tetrahydroindenyl group; 4,5,6,7-tet
Lahydro-1,2,3 trimethylindenyl group, etc.
And a substituted fluorenyl group is, for example, methyl fluorenyl
Group, dimethylfluorenyl group, tetramethylfluoride
And an octamethylfluorenyl group. Replacement tet
Lahydrofluorenyl groups are, for example, 1,2,3,4-
Tetrahydrofluorenyl group; 9-methyl-1,2,2
A 3,4-tetrahydrofluorenyl group,
A tahydrofluorenyl group is, for example, 9-methyl-octyl.
And a tahydrofluorenyl group. Substituted hexahydroa
Examples of the zulenyl group include 1-methylhexahydro
Azulenyl group, 2-methylhexahydroazulenyl group,
1,2-dimethylhexahydroazulenyl group, 1,3-
Dimethylhexahydroazulenyl group, 1,2,3-tri
It is a methylhexahydroazulenyl group.

X ¹ is a σ ligand. Specifically, hydride, halogen, alkyl, silyl, aryl, arylsilyl, amide, aryloxy, alkoxy, silyloxy, phosphide, sulfide,
Acyl, cyanide, azide, acetylacetonate, etc.
And combinations thereof. Specific compounds include (t-butylamide) (tetramethylcyclopentadienyl) 1,2-ethanediylzirconium dichloride and (t-butylamide) (tetramethylcyclopentadienyl) 1,2-ethanediyltitanium dichloride. , (Methylamide) (tetramethylcyclopentadienyl) 1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) 1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethylcyclopentadiyl (Enyl) -methylene titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride, (t-butylamido)
Dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dimethyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dimethyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dibenzyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) Silane titanium dichloride, (phenyl phosphide) dimethyl (tetramethyl cyclopentadienyl) silane zirconium dibenzyl, (t-butyl amide) dimethyl (tetramethyl cycle Pentadienyl) silane titanium dichloride, (dimethylaminoethyl) tetramethyl - cyclopentadienyl titanium (III) dichloride, 9-
(Dimethylaminoethyl) octahydro-fluorenyltitanium (III) dichloride, (di-n-butylaminoethyl) tetramethyl-cyclopentadienyltitanium (III) dichloride, (dimethylaminomethyl) tetramethyl-cyclopentadienyl Titanium (III) dichloride, (dimethylaminopropyl) tetramethyl-cyclopentadienyl titanium (III) dichloride, and the like. (Iv) The π ligand R ¹⁰ represented by the following general formula (11) is
M ³ R ¹⁰ X ⁴ n (11) (wherein, M ³ represents a transition metal element belonging to Group 4 of the periodic table of elements and a lanthanoid metal element. R ¹⁰ represents π X ⁴ represents a hydrogen atom, a halogen atom, a carbon atom having 1 to 2 carbon atoms, and specifically represents a group having a cyclopentadienyl skeleton.
0 hydrocarbon group, C1-C20 alkoxy group, C1-C20 thioalkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C6-carbon
-20 represents a thioaryloxy group, an amino group, an alkylsilyl group, etc., and a plurality of X ⁴ may be the same or different. X ⁴ may be bonded to R ¹⁰ via a specific group. n represents the valence of M ^3.

Examples of the compound represented by the general formula (11) include a mono (cyclopentadienyl) transition metal compound, a mono (indenyl) transition metal compound, and a mono (fluorenyl) transition metal compound. The substituted cyclopentadienyl group is, for example, a cyclopentadienyl group substituted by one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group; 1,3-dimethylcyclopentane 1,2,3-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3-di (trimethylsilyl) cyclopenta Dienyl group; tertiary butyl cyclopentadienyl group; 1,3-di (tertiary butyl) cyclopentadienyl group; pentamethylcyclopentadienyl group. Also, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluoryl A octyl group, an octahydrofluorenyl group and a substituted octahydrofluorenyl group. Titanium is preferably used as the transition metal. Specific examples of the titanium compound include cyclopentadienyl trimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl tripropyl titanium, cyclopentadienyl tributyl titanium,
Methylcyclopentadienyltrimethyltitanium, 1,2
-Dimethylcyclopentadienyltrimethyltitanium,
1,2,4-trimethylcyclopentadienyltrimethyltitanium, 1,2,3,4-tetramethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, penta Methylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium, pentamethylcyclopentadienyltributyltitanium, cyclopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopentadienylmethyl Titanium dichloride, pentamethylcyclopentadienylethyl titanium dichloride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl diethyl titanium monochloride Lido, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethyl Cyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tripropoxide, pentamethylcyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopenta Dienylmethoxytitanium dichloride, cyclopentadienyldimethoxytitanium chloride, pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltrichloride Titanium titanium, pentamethylcyclopentadienylmethyldiethoxytitanium, indenyltitanium trichloride, indenyltitaniumtrimethoxide, indenyltitaniumtriethoxide, indenyltrimethyltitanium, indenyltribenzyltitanium, pentamethylcyclopentadienyl Titanium trithiomethoxide, pentamethylcyclopentadienyltitanium trithiophenoxide, (1,2,3,4,
5,6,7,8-octahydrofluorenyl) titanium trichloride, (1,2,3,4,5,6,7,8-octahydrofluorenyl) titanium trimethoxide and the like. (V) a compound represented by the following general formula (12)

[0047]

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(Wherein M ⁴ represents a transition metal element of Group 4 of the periodic table of elements, Cp represents a group having a cyclopentadienyl skeleton. Y ⁷ represents O, S, NR, PR or CR. ₂ or a neutral two-electron donating ligand selected from OR, SR, NR ₂ or PR ₂ , and B represents an atom of Group 14 of the periodic table of the element (provided that , R is in each case a moiety selected from hydrogen, alkyl, aryl, silyl, alkyl halide, aryl halide, and combinations thereof having up to 20 non-hydrogen atoms). X ⁵ and X ⁶ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl having 1 to 20 carbon atoms. Represents an oxy group or a disubstituted amino group having 2 to 20 carbon atoms, Et good be the same or different .R ¹¹ to R ¹⁶ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Or a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different. Further, they may be arbitrarily combined to form a ring. The group having a cyclopentadienyl skeleton in the above Cp means a cyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexagon. Hydroazulenyl, tetrahydroindenyl, substituted tetrahydroindenyl, tetrahydrofluorenyl, substituted tetrahydrofluorenyl,
It refers to an octahydrofluorenyl group, a substituted octahydrofluorenyl group and the like. Examples of B include a carbon atom, a silicon atom and a germanium atom, and among them, a carbon atom and a silicon atom are preferable.

Specific examples of the compound represented by the above general formula (12) include isopropylidene (cyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (Methylcyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium Dichloride, isopropylidene (trimethylcyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t-butyl-5-
Methyl-2-phenoxy) titanium dichloride, isopropylidene (n-propylcyclopentadienyl)
(3-t-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (primary butylcyclopentadienyl) (3-t-butyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (phenylcyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-
t-butyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-T-butyl-2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (3-t-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylcyclopentadienyl) (3-t-butyl -2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t-butyl-2-phenoxy) titanium dichloride, isopropylidene (n-
Propylcyclopentadienyl) (3-t-butyl-2
-Phenoxy) titanium dichloride, isopropylidene (primary butylcyclopentadienyl) (3-t-butyl-2-phenoxy) titanium dichloride, isopropylidene (phenylcyclopentadienyl) (3-t
-Butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadiene) Enyl) (2-phenoxy) titanium dichloride, isopropylidene (trimethylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (2
-Phenoxy) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (first
Tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (phenylcyclopentadienyl) (2-phenoxy) titanium dichloride, and the like. The same applies to compounds in which titanium is changed to zirconium or hafnium and compounds in which isopropylidene is changed to dimethylsilylene, diphenylsilylene, or methylene in the above specific examples. Further, compounds obtained by changing dichloride to dibromide, diiodide, dimethyl, dibenzyl, dimethoxide, and diethoxide can be similarly exemplified.

Among the above transition metal compounds, because of their excellent copolymerizability, general formula (5) or general formula (6)
It is preferable to produce the ethylene copolymer of the present invention using the compound represented by More preferably, the case where the general formula (6) is used.

(B) (a) Compound capable of forming an ionic complex by reacting with an oxygen-containing compound and / or (ii) a transition metal compound The component (b) of the polymerization catalyst used in the present invention includes: The compounds shown below can react with an oxygen-containing compound and / or a transition metal compound to form an ionic complex. (A) Oxygen-containing compound as a component Compound represented by the following general formula (2)

[0052]

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And / or general formula (3)

[0054]

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An oxygen-containing compound represented by the formula: In the above general formulas (2) and (3), R ^{1 to} R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups. Groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. R ^{1 to} R ⁵ may be the same or different, and R ⁶ and R ⁷ may be the same or different. Y ^{1 to} Y ⁵ each represent a Group 13 element of the periodic table, and specifically, B, Al,
Ga, In, and Tl are mentioned, and among them, B and Al are preferable. Y ^{1 to} Y ³ may be the same or different, and Y ⁴ and Y ⁵ may be the same or different. Also, a to d are numbers of 0 to 50, respectively, and (a + b) and (c + d) are each 1 or more. Each of a to d is preferably in the range of 1 to 20, and particularly preferably in the range of 1 to 5.

[0056] Suitable examples of oxygen containing compounds, in particular alkyl aluminoxane used as such a catalyst component, ¹
H-NMR aluminum methyl group (Al-CH ₃₎ observed in the spectral high magnetic field component in the methyl proton signal region based on the binding is of 50% or less. That is, when the ¹ H-NMR spectrum of the above contact product in a toluene solvent at room temperature was observed, it was found that “Al
The methyl proton signal based on “—CH ₃ ” is 1.0 to −0.5 ppm based on tetramethylsilane (TMS).
Seen in the range. TMS proton signal (0pp
m) is in the methyl proton observation region based on “Al—CH ₃ ”, and therefore, the methyl proton signal based on “Al—CH ₃ ” was measured based on 2.35 ppm of the methyl proton signal of toluene based on TMS. When divided into a magnetic field component (i.e., 0.1 to -0.5 ppm) and another magnetic field component (i.e., 1.0 to -0.1 ppm), the high magnetic field component is 50% or less of the whole, preferably The one having 45 to 5% can be suitably used as a catalyst component. (B) Compound capable of forming an ionic complex by reacting with a transition metal compound Examples of the compound capable of forming an ionic complex by reacting with a transition metal compound include an anion and a cation having a plurality of groups bonded to a metal. Or a Lewis acid. There are various coordination complex compounds comprising an anion and a cation having a plurality of groups bonded to a metal. For example, a compound represented by the following general formula (13) or (14) is preferably used. it can.

([L ¹ -H] ^{g +} ) _h ([M ⁵ X ⁷ X ⁸ ... X ⁿ ] ^(nm)- ) _i ... (13) ([L ² ] ^{g +} ) _h ([M ⁶ X ⁷ X ⁸ ... X ⁿ ] ^(nm)- ) _i ... (14) [In the formula (13) or (14), L ¹ is a Lewis base, and L ² is M ⁷ or R ¹⁷ described below. R ¹⁸ M ^8, a R ¹⁹ ₃ C or R ¹⁹ ₄ N, metal selected from 5 to group 15 of M ⁵ and M ⁶ are each periodic table, M ⁷ group 1 of the periodic table and group 8 ~ 12
M ⁸ is a metal selected from Groups 8 to 10 of the periodic table, and X ^{7 to} X ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, and a C 1 to C 20 group, respectively. It represents an alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group, or a halogen atom.
R ¹⁷ and R ¹⁸ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁹ represents an alkyl group. m is a valence of M ⁵ or M ⁶ and is an integer of 1 to 7, n is an integer of 2 to 8, g is L ¹ -H,
Ion valence of 1-7 integer L ^2, h is an integer of 1 or more,
i = h × g / (nm). ] Specific examples of M ⁵ and ^{M 6 B, Al, Si,} P, A
Ag, C are specific examples of each atom such as s and Sb, and M ^7.
Examples of each atom such as u, Na, Li, and M ⁸ are F
e, Co, Ni and the like. X ⁷ ~X ⁿ
Specific examples of the above include, for example, a dimethylamino group, a diethylamino group or the like as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group or the like as an alkoxy group, a phenoxy group, a 2,6-dimethylphenoxy group as an aryloxy group, 1 carbon atom such as naphthyloxy group
And an alkyl group having 6 to 20 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group. Examples of the alkyl group include phenyl, p-tolyl, benzyl, pentafluorophenyl, 3,5-di (trifluoromethyl) phenyl, 4-tert-butylphenyl, 2,6-dimethylphenyl, Examples of halogen such as 5-dimethylphenyl group, 2,4-dimethylphenyl group, and 1,2-dimethylphenyl group include F, Cl, Br,
I. Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of the substituted cyclopentadienyl group represented by each of R ¹⁷ and R ¹⁸ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

In the present invention, a plurality of groups are bonded to a metal.
As the anion, specifically, B (C₆F_Five)_Four ^-, B
(C₆HF_Four)_Four ^-, B (C₆H_TwoF_Three)_Four ^-, B (C₆H
_ThreeF _Two)_Four ^-, B (C₆H_FourF)_Four ^-, B (C₆(CF_Three)
F_Four)_Four ^-, B (C₆H_Five)_Four ^- , PF₆ ^-, P (C₆F_Five)
₆ ^-, Al (C₆HF_Four)_Four ^-And the like. Also,
As the metal cation, Cp_TwoFe⁺, (MeCp)_Two
Fe⁺, (TBuCp)_TwoFe⁺, (Me_TwoCp)_TwoF
e⁺, (Me_ThreeCp)_TwoFe⁺, (Me_FourCp)_TwoFe
⁺, (Me_FiveCp)_TwoFe⁺, Ag⁺, Na⁺, Li⁺
And other cations include pyridi
, 2,4-Dinitro-N, N-diethylanilini
, Diphenylammonium, p-nitroanilinium
, 2,5-dichloroaniline, p-nitro-N, N-
Dimethylanilinium, quinolinium, N, N-dimethyl
Luanilinium, N, N-diethylanilinium, N,
N, N-trimethylanilinium, N-methyl-2-cy
Ano-pyridinium, N-benzyl-4-cyano-pyri
Nitrogen-containing compounds such as dinium, triphenylcarbeni
, Tri (4-methylphenyl) carbenium, tri
Carbeni such as (4-methoxyphenyl) carbenium
Compound, CH_ThreePH_Three ⁺, C_TwoH_FivePH _Three ⁺, C_Three
H₇PH_Three ⁺, (CH_Three)_TwoPH_Two ⁺, (C_TwoH_Five)_Two
PH_Two ⁺, (C_ThreeH₇)_TwoPH_Two ⁺, (CH_Three)_ThreePH
⁺, (C_TwoH_Five)_ThreePH⁺, (C_ThreeH ₇)_ThreePH⁺,
(CF_Three)_ThreePH⁺, (CH_Three)_FourP⁺, (C_TwoH_Five)
_FourP⁺, (C_ThreeH₇)_FourP⁺Alkylphosphoni such as
Um ion and C₆H_FivePH_Three ⁺, (C₆H_Five)_TwoP
H_Two ⁺, (C₆H_Five)_ThreePH⁺, (C₆H_Five)_FourP⁺,
(C_TwoH_Five)_Two(C₆H_Five) PH⁺, (CH_Three) (C₆
H_Five) PH_Two ⁺, (CH_Three)_Two(C₆H_Five) PH⁺,
(C_TwoH_Five)_Two(C₆H_Five)_TwoP⁺Arylpho
Sponium ions and the like can be mentioned.

Among the compounds of the general formulas (13) and (14),
Specifically, the following can be particularly preferably used. Examples of the compound of the general formula (13) include triethylammonium tetraphenylborate and tri (n) tetraphenylborate.
-Butyl) ammonium, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, tetrakis (pentafluorophenyl) borate Pyridinium, pyrrolium tetra (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate N, N
-Dimethylanilinium, methyldiphenylammonium tetrakis (pentafluorophenyl) borate and the like. On the other hand, examples of the compound of the general formula (14) include ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate,
Ferrocenium tetrakis (pentafluorophenyl) borate, decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate,
Cyanoferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, trityl tetraphenylborate, trityl tetrakis (pentafluorophenyl) borate, silver hexafluoroarsenate, hexafluoroantimonic acid Silver, silver tetrafluoroborate, tetrakis (pentafluorophenyl) borate-N, N, N-trimethyl quaternary ammonium salt, tetrakis (pentafluorophenyl) borate-N-methyl-2-cyanopyridinium salt and the like can be mentioned.

As the Lewis acid, for example, B (C ₆ F
₅ ) ₃ , B (C ₆ HF ₄ ) ₃ , B (C ₆ H ₂ F ₃ ) ₃ , B (C _{6
H 3 F 2) 3, B} (C 6 H 4 F) 3, B (C 6 (CF 3) F 4)
₃ , P (C ₆ F ₅ ) ₅ , Al (C ₆ HF ₄ ) _{3 and the} like can also be used. In the polymerization catalyst of the present invention, as the component (b), only the oxygen-containing compound of the component (a) may be used alone or in combination of two or more. Singly or in combination of two or more compounds capable of forming an ionic complex. Alternatively, the component (a) and the component (b) may be used in an appropriate combination. (C) As the alkylating agent alkylating agents there are various, for example, the general formula _{^{(15) R 20 m Al (}} OR 21) n X 9 3-mn ··· (15) [wherein, R ²⁰ and R ²¹ each represent an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms, and X ⁹ represents a hydrogen atom or a halogen atom. Further, m is 0 <m ≦ 3, preferably 2 or 3, and most preferably 3.
≦ n <3, preferably 0 or 1. Alkyl group-containing aluminum compounds or general formula _{^{(16) R 20 2 Mg ···}} (16) wherein represented by], R ²⁰ is as defined above. Alkyl group-containing magnesium compound represented by], yet the general formula _{^{(17) R 20 2 Zn ···}} (17) wherein, R ²⁰ is as defined above. And the like.

Among these alkyl group-containing compounds, alkyl group-containing aluminum compounds, particularly trialkylaluminum and dialkylaluminum compounds, are preferred. (2) Preparation method of catalyst As a method for contacting the components (a) and (b) with the component (c) optionally used in the catalyst to be subjected to polymerization, for example, the components (a) and (b) A method in which the component (c) is added to the contact mixture as a catalyst to be brought into contact with each monomer to be polymerized, and the component (a) is added to the contact mixture of the components (b) and (c) to form a catalyst, A method of contacting a monomer to be polymerized, a method of adding a component (b) to a contact mixture of a component (a) and a component (c) to make a catalyst, and contacting the monomer component to be polymerized; , (B) and (c) are separately brought into contact, and a catalyst is prepared by contacting the contact mixture of the monomer component to be polymerized with the (c) component with the catalyst prepared in the above (1).

The contact between the components (a) and (b) and the component (c) optionally used can be carried out at a polymerization temperature or in a range of -20 to 200 ° C. . Further, before introducing each component of the catalyst, an organic aluminum such as triisobutylaluminum may be added to capture impurities. (3) Polymerization Method The polymerization method for producing the ethylene copolymer of the present invention is not particularly limited, and bulk polymerization may be used. Aliphatic hydrocarbons such as pentane, hexane and heptane, and alicyclic hydrocarbons such as cyclohexane may be used. Hydrogen or benzene, toluene,
It may be carried out in an aromatic hydrocarbon solvent such as xylene or ethylbenzene.

Specifically, a diene monomer (C) or an aromatic vinyl monomer (D) is dissolved in these solvents, an oxygen-containing compound is added, and the mixture is pressurized to a desired pressure with an α-olefin and ethylene. After that, a method of adding a transition metal compound and polymerizing can be exemplified. The proportion of the catalyst component used in the polymerization is not particularly limited, but (a)
When the transition metal compound and the oxygen-containing compound (a) are used as the catalyst component (b), the amount of (a) is preferably from 1 to 10 ⁶ moles, more preferably 1 mole, of (a).
The amount of (a) is in the range of 10 to 10 ⁴ moles per 1 mole of (a). Outside this range, the polymerization activity may decrease. When the compound (b) is used as the (a) transition metal compound and the catalyst component (b), the amount of (b) is preferably from 1 to 2 × 10 ³ moles per 10 to 1 mole of (a), More preferably, (b) to 5 to 1 mol of (a)
Is in the range of 1 to 10 ³ mol. Outside this range,
The polymerization activity may decrease. When (a) a transition metal compound and (c) an alkylating agent are used, (a) 1
The molar ratio of (c) is preferably from 1 to 1 × 10 ⁴ mol, more preferably 5 mol of (c) per mol of (a).
２2 × 10 ³ mol. Particularly preferably,
(A) is in the range of 10 to 1 × 10 ³ mol of (c) per 1 mol. If (c) exceeds 1 × 10 ⁴ mol, the alkylating agent may remain, which is not preferable. If (c) is less than 1 mol, the polymerization activity may decrease.

The amount of the monomer and (a) the transition metal compound
Is used, the total amount of the monomers is 1 to 1 × 10^TenMo
(A) 1 mole of the transition metal compound is used
Preferably, the total amount of the monomers is 1
~ 1 × 10⁸1 mole of transition metal compound (a) per mole
, Particularly preferably, the total amount of the monomers is 1 to 1 × 10 ⁶
(A) 1 mole of the transition metal compound per mole
You. In this case, the catalyst component (b) or the catalyst component (c)
The use ratio can be appropriately selected and used within the above range.
Wear.

The polymerization temperature is not particularly limited, but is generally 0 to 200 ° C., preferably 20 to 100 ° C.
The polymerization pressure is not particularly limited, but is generally from normal pressure to 1
5 MPa, preferably normal pressure to 5 MPa. In order to control the molecular weight, a chain transfer agent such as hydrogen may be added during polymerization. In addition, in the obtained ethylene copolymer, the content ratio of the repeating unit derived from each monomer can be appropriately controlled by the amount of each monomer used for polymerization. Specifically, the charged amount of the diene monomer to the solvent (molar ratio to the solvent) is usually 0.001 to 10 mol%. Preferably, it is 0.005 to 5 mol%. More preferably,
0.01 to 3 mol%. If the amount is less than 0.001 mol%, the diene monomer will not sufficiently polymerize. Also, 1
If it exceeds 0 mol%, crosslinking is excessive.

The reaction rate of the diene monomer (the amount of the diene monomer unit contained in the polymer with respect to the amount of the diene monomer initially charged) is usually 0.1 to 60% mol. Preferably, it is 0.5 to 50 mol%. More preferably, it is 1 to 40 mol%. 0.1 mol%
If it is less than 3, the diene monomer does not crosslink. Also,
If it exceeds 60 mol%, crosslinking is excessive.

[0067]

Next, the present invention will be described in more detail by way of examples. These are illustrative and the invention is not limited in any way by these examples. Example 1 200 ml of dehydrated toluene, 50 mmol of purified para-3-butenylstyrene treated with activated alumina, 0.5 mmol of triisobutylaluminum, 0.5 mmol of methylaluminoxane (manufactured by Albemarle Co., Ltd.) were placed in a dry 1 liter pressure-resistant polymerization tank. 5 in aluminum concentration
After charging mmol and 600 micromoles of triethylaluminum, propylene was charged until the gauge pressure reached 0.2 MPa, and then ethylene was charged until the gauge pressure reached 0.9 MPa. Thereafter, (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride was added at 2 μmol in zirconium concentration, and polymerization was started at 30 ° C. Thereafter, every time ethylene and propylene are consumed and the gauge pressure drops to 0.5 MPa, the operation of charging propylene to a gauge pressure of 0.6 MPa and then charging ethylene to a gauge pressure of 0.9 MPa is repeated, and polymerization is performed for 7 minutes. did.

After the polymerization, ethylene and propylene are degassed,
A small amount of methanol was added to terminate the polymerization. The obtained viscous solution was precipitated in methanol, and the polymer was recovered and dried at 50 ° C. under reduced pressure to obtain 7.6 g of an ethylene copolymer. ^The composition obtained from ¹ H-NMR was as follows: ethylene / propylene / para-3-butenylstyrene = 86.4
2 / 16.93 / 0.65 (mol%). Para-3-
The amount of the butenylstyrene unit is calculated from the peak derived from the phenyl group on ¹ H-NMR. Also ¹
H-NMR confirmed that a vinyl group bonded to a phenyl group was present in the molecular chain, and the amount of unreacted vinyl group units of para-3-butenylstyrene / the amount of para-3-butenylstyrene units The ratio of the amounts is 0.862, and the above (1)
The ratio K of partial cross-linking determined by the formula was 13.8%.

From the infrared absorption spectrum (IR) of this copolymer, only absorption of stretching vibration of a carbon-carbon double bond bonded to a phenyl group was observed at 1630 cm ⁻¹ , and this vinyl group was found to be para-3 -It was confirmed to be a styrene residue of butenyl styrene. The intrinsic viscosity [η] of the obtained ethylene-based copolymer measured at 135 ° C. in decalin was 2.31, and the molecular weight distribution (M
w / Mn) was 2.07.

[Embodiment 2] In Embodiment 1, para-3-
Example 1 was repeated except that 40 mmol of divinylbenzene was used instead of butenylstyrene and the amount of triethylaluminum was 200 μmol.
1.3 g of an ethylene copolymer was obtained. The composition of the ethylene copolymer obtained from ¹ H-NMR was ethylene / propylene / divinylbenzene (derived from phenyl group) = 67.9.
9 / 31.27 / 0.35 (mol%). The ratio of the amount of unreacted vinyl group units to the amount of divinylbenzene units in divinylbenzene was 0.657, and the ratio K of partial crosslinking was 34.3%.

[Η] of the obtained ethylene copolymer measured in decalin at 135 ° C. was 3.24, and the molecular weight distribution (Mw / Mn) by GPC measurement was 2.17. [Example 3] In Example 2, instead of (1,2'-ethylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,1'-ethylene) (2,2'- Ethylene) -bis (indenyl)
Except using zirconium dichloride, it carried out similarly to Example 2 and obtained 7.0 g of ethylene-type copolymers.

The composition of the ethylene copolymer obtained from ¹ H-NMR was as follows: ethylene / propylene / divinylbenzene (derived from phenyl group) = 70.28 / 29.44 / 0.28
(Mol%). The ratio of the amount of unreacted vinyl group units of divinylbenzene / the amount of divinylbenzene units is 0.750.
And the ratio K of partial crosslinking was 25.0%. [Η] of the obtained ethylene-based copolymer measured at 135 ° C. in decalin was 3.04, and the molecular weight distribution (Mw / Mn) by GPC measurement was 2.56.

Example 4 200 ml of dehydrated toluene, 40 mmol of purified para-3-butenylstyrene treated with activated alumina, 0.5 mmol of triisobutylaluminum, and methyl were placed in a dry 1 liter pressure-resistant polymerization tank. Aluminoxane (Albemarle)
Was introduced at an aluminum concentration of 5 mmol, propylene was introduced at a gauge pressure of 0.2 MPa, and ethylene was introduced at a gauge pressure of 0.9 MPa. Thereafter, 2 micromol of racemic-ethylenebisindenyl zirconium dichloride was added at a zirconium concentration, and polymerization was started at 30 ° C. Thereafter, every time ethylene and propylene are consumed and the gauge pressure decreases to 0.5 MPa, the operation of charging propylene to a gauge pressure of 0.6 MPa, and then repeating the operation of charging ethylene to a gauge pressure of 0.9 MPa, is repeated for 7 minutes. did.

After the polymerization, ethylene and propylene are degassed.
A small amount of methanol was added to terminate the polymerization. The resulting viscous solution was precipitated in methanol, and the polymer was recovered. The polymer was dried under reduced pressure at 50 ° C. to obtain 27.0 g of an ethylene copolymer. ^The composition obtained from ¹ H-NMR was ethylene / propylene / para-3-butenylstyrene = 8
1.17 / 18.28 / 0.55 (mol%).
The amount of para-3-butenylstyrene unit was calculated from a peak derived from a phenyl group on ¹ H-NMR. Further, ¹ H-NMR confirmed that a vinyl group bonded to a phenyl group was present in the molecular chain.
The ratio of the amount of the unreacted vinyl group unit of 3-butenylstyrene / the amount of the para-3-butenylstyrene unit is 0.945, and the ratio K of the partial cross-linking obtained from the above formula (1) is:
It was 5.5%.

The infrared absorption spectrum of the copolymer
1630cm from IR (IR) analysis ^-1To a phenyl group
Only absorption of stretching vibration of combined carbon-carbon double bond confirmed
This vinyl group is substituted with para-3-butenylstyrene.
It was confirmed that it was a tylene residue. Ethylene obtained
[Η] of the system copolymer measured at 135 ° C. in decalin is
1.53, which is the molecular weight distribution (Mw /
Mn) was 4.61.

[Embodiment 5] In Embodiment 4, para-3-
Example 4 was repeated except that 40 mmol of divinylbenzene was used instead of butenylstyrene.
6.0 g of an ethylene copolymer was obtained. The composition of the ethylene copolymer obtained from ¹ H-NMR was ethylene / propylene / divinylbenzene (derived from phenyl group) = 79.2.
6 / 20.61 / 0.13 (mol%).

The ratio of the amount of unreacted vinyl group units of divinylbenzene / the amount of divinylbenzene units was 0.846,
The ratio K of partial crosslinking was 15.4%. [Η] of the obtained ethylene copolymer was measured in decalin at 135 ° C.
Is 1.26, and the quantity distribution (Mw /
Mn) was 1.90. Example 6 The procedure of Example 5 was repeated, except that meso-ethylenebisindenyl zirconium dichloride was used instead of racemic-ethylenebisindenyl zirconium dichloride. A polymer was obtained.

The composition of the ethylene copolymer obtained from ¹ H-NMR was: ethylene / propylene / divinylbenzene (derived from phenyl group) = 76.02 / 23.87 / 0.11
(Mol%). The ratio of the amount of unreacted vinyl group units of divinylbenzene / the amount of divinylbenzene units is 0.818.
And the ratio K of partial cross-linking was 18.2%.

[Η] of the obtained ethylene copolymer measured at 135 ° C. in decalin was 1.11, and the molecular weight distribution (Mw / Mn) by GPC measurement was 2.25. Example 7 In a dry 1 liter pressure-resistant polymerization tank, 350 ml of dehydrated toluene, 53 mmol of purified divinylbenzene treated with activated alumina, 0.5 mmol of triisobutylaluminum, and methylaluminoxane (manufactured by Albemarle Co.) were subjected to aluminum concentration. 3 mmol,
After charging 480 micromoles of triethylaluminum, propylene was charged to a gauge pressure of 0.2 MPa, and then ethylene was charged to a gauge pressure of 0.9 MPa. Then, 3 μmol of (η ⁵ -1,2,3,4-tetrahydro-9-fluorenyl) (t-butylamido) dimethylsilanetitanium dichloride was added at a titanium concentration of 70 μm, and
Polymerization was started at ℃. Thereafter, every time ethylene and propylene are consumed and the gauge pressure is reduced to 0.5 MPa, propylene is charged to the gauge pressure of 0.6 MPa,
Subsequently, the operation of charging ethylene up to 0.9 MPa at a gauge pressure was repeated, and polymerization was carried out for 30 minutes.

After depolymerization of ethylene and propylene after polymerization,
A small amount of methanol was added to terminate the polymerization. The resulting viscous solution was precipitated in methanol, and the polymer was recovered. The polymer was dried at 50 ° C. under reduced pressure to obtain 18.5 g of an ethylene copolymer. ^The composition obtained from ¹ H-NMR is ethylene / propylene / divinylbenzene (derived from phenyl group) =
72.76 / 26.02 / 1.22 (mol%).

From ¹ H-NMR, it was confirmed that a vinyl group bonded to a phenyl group was present in the molecular chain, and the ratio of the amount of unreacted vinyl group units of divinylbenzene / the amount of divinylbenzene units was observed. Was 0.754, and the bridge ratio K of the partial bridge obtained from the above equation (1) was 24.6%. 135 of the obtained ethylene copolymer in decalin
[Η] measured at ° C. was 2.80, and the molecular weight distribution (Mw / Mn) by GPC measurement was 5.31.

Example 8 Toluene 2 in Example 1
The procedure of Example 1 was repeated, except that 100 ml of toluene and 100 ml of styrene were used instead of 00 ml, 40 mmol of para-3-butenylstyrene was used, and the polymerization time was 60 minutes. A copolymer was obtained.

The composition of the ethylene copolymer obtained from ¹ H-NMR and pyrolysis GC mass spectrum was as follows: ethylene / propylene / styrene / para-3-butenylstyrene (derived from phenyl group) = 79.12 / 18 .04 / 2.45 /
0.39 (mol%). The ratio of the amount of unreacted vinyl group units of para-3-butenylstyrene / the amount of para-3-butenylstyrene units of the obtained ethylene copolymer was 0.795, and from the above formula (1), The determined percentage K of partial crosslinking was 20.5%.

[Η] of the obtained ethylene copolymer measured in decalin at 135 ° C. was 2.12, and the molecular weight distribution (Mw / Mn) by GPC measurement was 2.11. Example 9 The procedure of Example 4 was repeated, except that 150 ml of toluene and 50 ml of styrene were used instead of 200 ml of toluene, 40 mmol of para-3-butenylstyrene was used, and the polymerization time was 60 minutes. In the same manner as described above, 3.2 g of an ethylene copolymer was obtained.

The composition of the ethylene copolymer obtained from ¹ H-NMR and pyrolysis GC mass spectrum was as follows: ethylene / propylene / styrene / para-3-butenylstyrene (derived from phenyl group) = 77.28 / 21 .61 / 0.53 /
0.58 (mol%). The ratio of the amount of unreacted vinyl group units of para-3-butenylstyrene / the amount of para-3-butenylstyrene units in the obtained ethylene copolymer was 0.621. The determined percentage K of partial crosslinking was 37.9%.

[Η] of the obtained ethylene copolymer measured at 135 ° C. in decalin was 3.34, and the molecular weight distribution (Mw / Mn) by GPC measurement was 2.91. Example 10 The procedure of Example 7 was repeated, except that 350 ml of toluene was used instead of 350 ml of toluene, and 5 ml of styrene treated with activated alumina was used. I got

The composition of the ethylene-based copolymer obtained from ¹ H-NMR and pyrolysis GC mass spectrum was as follows: ethylene / propylene / styrene / para-3-butenylstyrene (derived from phenyl group) = 72.46 / 25 .68 / 0.92 //
0.94 (mol%). The divinylbenzene unit is calculated from the peak derived from the phenyl group. The ratio of the amount of unreacted vinyl group units of divinylbenzene / the amount of divinylbenzene units in the obtained ethylene copolymer was 0.553, and the bridge ratio K of the partial bridge obtained from the above equation (1) was: It was 44.7%. The [η] of the obtained ethylene copolymer measured at 135 ° C. in decalin was 2.5.
4 and molecular weight distribution (Mw / Mn) by GPC measurement
Was 4.27.

[0088]

The ethylene copolymer obtained according to the present invention has a partially crosslinked structure and also has an uncrosslinked reactive vinyl group. It has excellent toughness, elongation, rigidity and compatibilizing ability, and is useful as a macromonomer for obtaining syndiotactic polystyrene graft copolymers useful as composite materials and heat-resistant elastomers, as well as syndiotactic. It is extremely useful as a material for obtaining a compatibilizer in a composition of a polystyrene and a rubber component or a general composition of a polystyrene and a rubber component. Further, the ethylene-based copolymer can be efficiently obtained by the production method of the present invention.

────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl ⁶ identification symbol FI C08F 210:. 04)

Claims (8)

[Claims] 1. A diene monomer having at least one ethylene (A), at least one α-olefin having 3 to 30 carbon atoms (B) and at least one styrene vinyl group, or at least one diene having a conjugated ene. A copolymer of the system monomer (C), wherein the molar ratio of ethylene (A) / α-olefin (B) is 20/80 to 97/3;
When the total amount of the repeating units derived from the components (A) to (C) is 100 mol%, the repeating unit derived from the diene monomer (C) is 0.001 to 20 mol%, and the following ( 1) An ethylene copolymer having a vinyl group derived from a diene monomer in a molecular chain in which a ratio K of partial crosslinking derived from the diene monomer represented by the formula is 0.1 to 80%. (Equation 1) 2. An ethylene (A), at least one α-olefin having 3 to 30 carbon atoms (B), at least one diene monomer having a styrene-based vinyl group, or a diene having at least one conjugated ene. A copolymer of a system monomer (C) and at least one aromatic vinyl monomer (D), wherein the molar ratio of ethylene (A) / α-olefin (B) is 20/80 to 97/3;
When the total amount of the repeating units derived from the components (A) to (D) is 100 mol%, the repeating units derived from the diene monomer (C) are 0.001 to 20 mol%, and the aromatic vinyl monomer (D ) Is from 0.01 to 30.
Ethylene having a vinyl group derived from a diene monomer in a molecular chain having a mole percentage of 0.1 to 80% of a partial crosslink derived from the diene monomer represented by the above formula (1). Based copolymer. 3. An α-olefin having 3 to 30 carbon atoms (B)
Is an ethylene copolymer according to claim 1 or 2. 4. The ethylene copolymer according to claim 1, wherein the vinyl group derived from the diene monomer is a styrene vinyl group. (5) (a) a transition metal compound, (b) (a) a general formula (2) (Wherein, R ^{1 to} R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ^{1 to} Y ³ each represent a Group 13 element of the periodic table,
They may be the same or different, a and b each represent a number of 0 to 50, and a + b is 1 or more. ) And / or general formula (3) (Wherein, R ⁶ and R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ⁴ and Y ⁵ each represent a Group 13 element in the periodic table, They may be the same or different, c
And d each represent a number from 0 to 50, and c + d is 1 or more. And / or (b) a catalyst formed using a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (a). The method for producing an ethylene-based copolymer according to any one of claims 1 to 4, wherein (6) The transition metal compound represented by the following general formula:
6. The method according to claim 5, wherein:
3. The method for producing an ethylene copolymer according to item 1. Embedded image[Where M¹Is group 3 to 10 of the periodic table or lanthanoid
Indicates the metal element of the column, E ¹And E^TwoAre the replacement symbols
Lopentadienyl group, indenyl group, substituted indenyl
Group, fluorenyl group, substituted fluorenyl group, hexahydric
Loazulenyl group, substituted hexahydroazulenyl group, tet
Lahydroindenyl group, substituted tetrahydroindenyl
Group, tetrahydrofluorenyl group, substituted tetrahydrofuran
Fluorenyl group, octahydrofluorenyl group, substituted octane
Tahydrofluorenyl group, heterocyclopentadienyl
Group, substituted heterocyclopentadienyl group, amide group,
Selected from sulfide groups, hydrocarbon groups and silicon-containing groups
Ligand¹And A^TwoForm a crosslinked structure through
And they are the same or different
May be X¹Represents a σ-binding ligand, and X¹Is multiple
If there is more than one X¹May be the same or different,
Other X¹, E¹, E^TwoOr Y⁶And may be crosslinked.
Y⁶Represents a Lewis base;⁶If there are multiple
Y⁶May be the same or different, and the other Y⁶, E¹,
E^TwoOr X¹May be cross-linked with A¹And A^TwoHaso
Each represents a cross-linking group comprising a hydrocarbon group having 1 or more carbon atoms.
However, they may be identical or different. q
Is an integer of 1 to 5 [(M¹Valence-2), and r
Represents an integer of 0 to 3. ] 7. The method according to claim 5, wherein (a) the transition metal compound is represented by the following general formula (5).
3. The method for producing an ethylene copolymer according to item 1. Embedded image (Wherein E ³ and E ⁴ are unsubstituted or substituted cyclopentadienyl groups, indenyl groups, substituted indenyl groups,
Fluorenyl, substituted fluorenyl, hexahydroazulenyl, substituted hexahydroazulenyl, tetrahydroindenyl, substituted tetrahydroindenyl, tetrahydrofluorenyl, substituted tetrahydrofluorenyl, octahydrofluorenyl , A substituted octahydrofluorenyl group, wherein A ³ and A ⁴ are a hydrogen atom,
C1-C10 alkyl group, or C6-C6 respectively
20 aryl groups, alkylaryl groups, arylalkyl groups or halogenated aryl groups, or a hydrocarbon group having 1 to 20 carbon atoms containing a heteroatom selected from oxygen, nitrogen, sulfur or silicon, and Q is E ³ And E ⁴ are a C 2-10 hydrocarbon group or a C 1-10 hydrocarbon group containing silicon, germanium or tin, or carbon, silicon, germanium or tin atom, and A ³ and A ⁴ is connected to each other and A ³ ,
A ⁴ and Q may form a ring structure. R ⁸ and R ^{9 each} represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a silicon-containing alkyl group,
20 aryl group, alkylaryl group or arylalkyl group, and M ² is titanium, zirconium or hafnium. ) 8. The method according to claim 1, wherein (a) the transition metal compound has the following general formula:
6. The method according to claim 5, wherein:
3. The method for producing an ethylene copolymer according to item 1. Embedded image(Where M^TwoIs titanium, zirconium or hafnium
Yes, Cp^*Is M^TwoTo η^FiveCyclo bonded in a bonding mode
Pentadienyl group, substituted cyclopentadienyl group or i
Ndenyl group, substituted indenyl group, fluorenyl group, substituted
Fluorenyl group, hexahydroazulenyl group, substituted hex
Sahydroazulenyl group, tetrahydroindenyl group,
Substituted tetrahydroindenyl group, tetrahydrofluorenyl
Group, substituted tetrahydrofluorenyl group, octahydro
A fluorenyl group or a substituted octahydrofluorenyl group
You. X¹Represents a σ ligand; n is 1 or 2;
X ¹May be the same or different,
It may be bonded via any group. Y⁷Is O,
S, NR, PR or CR_TwoOr OR, SR,
NR_TwoOr PR_TwoNeutral two-electron donating donor selected from
And Z is SiR_Two, CR_Two, SiR_TwoSiR
_Two, CR_TwoCR_Two, CR = CR, CRSiR_Two, GeR
_Two, BR, BR_TwoWhere R is each
In some cases, hydrogen, an alkyl group, an aryl group, a silyl group,
Alkylated halogenates, aryl halides, and the like
Not more than 20 non-hydrogens, consisting of at least two combinations
It is selected from the group consisting of those having atoms. Sa
Furthermore, two or more of the R groups may be Z or Y⁷And Z
May form a fused ring system. )