JP2000072825A - Ethylenic copolymer, its production, and resin composition, molded product and lubricant containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer consisting of ethylene and an α-olefin, useful as a modifying agent for resins and a lubricant component having excellent viscosity index and pour point and contained in a resin composition having excellent flexibility, transparency, low temperature shock resistance and mechanical strength. SOLUTION: This copolymer is such one as to satisfy (1) the equations 1<=α<55 ([EAE]/[EAA])/[(100-α)/α]>1.0 and l<=α<55 wherein [EAE] and [EAA] are triad chain distribution, as measured by 13C nuclear magnetic resonance spectra, of (E) ethylene and (A) an α-olefin and α is the α-olefin content (mol.%) as measured by 13C nuclear magnetic resonance spectrum, and (2) [η]as 0.01-20 (dl/g) wherein η is the ultimate viscosity measured at 135 deg.C after dissolving in decalin. It is preferable that the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of this copolymer satisfies the relation 2.1<Mw/Mn<=4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ethylene / α-olefin copolymer useful as a resin modifier and a lubricating oil component, a method for producing the same, a resin composition containing the same, a molded article, and a lubricating oil. It is. The resin composition and the molded article are excellent in flexibility, transparency and impact resistance, especially in low-temperature impact resistance and mechanical strength, and the lubricating oil is excellent in viscosity index and pour point.

[0002]

2. Description of the Related Art Olefin polymers, in particular, polypropylene, which is a crystalline polymer, are excellent in rigidity, tensile strength, heat resistance, chemical resistance, optical properties, workability, etc., and have a lower specific gravity than polystyrene. It is widely used in the fields of injection molded products, containers, packaging materials and the like.

[0003] On the other hand, there is a disadvantage that the impact resistance, especially at low temperatures, is poor. Therefore, in order to improve the impact resistance, random polypropylene or block polypropylene copolymerized with ethylene was studied, but the former is superior in impact resistance at room temperature and transparency, but has reduced rigidity, In addition, the impact resistance at low temperatures has not been improved, and the latter has a somewhat improved balance of stiffness and impact resistance at low temperatures, but the impact resistance at low temperatures is sufficient due to the uneven copolymer composition. I couldn't say. As described above, it is difficult to balance transparency, rigidity, and low-temperature impact resistance with a polypropylene-based resin alone, and attempts have been made to improve the composition with other resins.

Japanese Patent Publication No. 58-38459 discloses that 40 to 80% by weight of polypropylene, 15 to 50% by weight of ethylene / butene-1 copolymer, and 0 to 15% of low density polyethylene.
In weight percent compositions are disclosed. In the composition, the impact resistance and the low-temperature embrittlement are improved, but the rigidity is reduced. Japanese Patent Publication No. 4-10504 discloses that 0.5 to 50 parts by weight of an ethylene / butene-1 copolymer and 0.0 to 50 parts by weight of a sorbitol derivative per 100 parts by weight of polypropylene.
Compositions comprising 1-4 parts by weight are disclosed. transparency,
Improved impact resistance, but low rigidity.

Japanese Patent Publication No. 6-45731 discloses that 50 to 95% by weight of polypropylene and 85 to 9% of ethylene are contained.
5 mol%, weight average molecular weight 30,000-200,000, Mw / Mn = 2
Ethylene and two melting peaks by DSC
A composition comprising 5 to 50% by weight of a butene-1 copolymer is disclosed. Although the low-temperature impact strength is good, the rigidity is low and the transparency is not sufficient.

JP-A-63-193945 discloses that 50 to 95% by weight of a random polypropylene having an ethylene content of 0.5 to 15% by weight, 2 to 15% by weight of a total ethylene content and 50% by weight of an ethylene content of a rubber portion. 5 to 40% by weight of a block polypropylene having a melt index MI of 1 or more and a density of 0.880 to 0.8%.
A composition comprising 1 to 15% by weight of an ethylene / α-olefin copolymer having a weight of 930 g / cm ³ is disclosed.
It has a good balance of transparency, impact resistance and flexural rigidity, but has low low-temperature impact resistance as shown in the examples.

Japanese Patent Application Laid-Open No. 1-247444 discloses that 40 to 95% by weight of a crystalline propylene polymer or copolymer containing 1 to 100,000 ppm of an α-olefin having 6 or more carbon atoms or vinylcycloalkane, Is a polymer 5 having a refractive index difference of -0.010 to 0.0150.
A composition comprising 60% by weight is disclosed. transparency,
Although the elastic modulus and the impact resistance at normal temperature are good, the low-temperature impact resistance is low.

As described above, these compositions have not been sufficiently satisfactory in terms of balance between transparency, rigidity and low-temperature impact resistance. Further, regarding the cold resistance, flexibility, transparency and impact resistance of a polypropylene resin, a method of adding a small amount of an ethylene / α-olefin elastomer represented by an ethylene / propylene elastomer has been used. For example, a method of adding an ethylene / propylene copolymer (Japanese Patent Publication No. 35-7088),
A method of adding an ethylene / butene-1 copolymer having an ethylene content of 75 to 30 mol% (JP-B-38-7240, JP-B-43-24526, etc.) may be mentioned.
However, although the impact resistance is improved by these methods, there are problems such as deterioration in tensile strength and transparency. Further, as a method for obtaining a polypropylene composition having good transparency and impact resistance, a method of adding a specific ethylene / α-olefin copolymer to polypropylene is disclosed (Japanese Patent Application Laid-Open No. 52-72744).

Recently, a method of improving the impact resistance and transparency by adding a small amount of an ethylene / α-olefin elastomer obtained from a metallocene compound to polypropylene has been disclosed (Japanese Patent Application Laid-Open No. 62-121709). JP, JP-A-6-192500, JP-A-6-339
920). However, the compositions obtained by these methods are excellent in impact resistance, transparency, and low-temperature embrittlement, but have a drawback of poor flexibility. When flexibility is required, it is necessary to increase the ratio of the ethylene / α-olefin elastomer to be blended, but the polypropylene and the ethylene / α-olefin elastomer have poor compatibility, and the obtained resin composition is transparent. In addition to poor impact resistance and strength properties, it also has the problem of whitening when subjected to an impact, impairing its commercial value, etc., and has poor impact resistance, flexibility, transparency, whitening resistance, and mechanical strength. Was enough.

Also disclosed is a method for improving cold resistance, whitening resistance, impact resistance and transparency by adding an ethylene / α-olefin elastomer having specific properties obtained by a metallocene compound to polypropylene. (Japanese Patent Application Laid-Open Nos. 8-269258 and 8-269263). However, the compositions obtained by these methods are excellent in cold resistance, whitening resistance, impact resistance, and transparency, but have a drawback of poor low-temperature impact resistance.

An example in which an ethylene / α-olefin copolymer is used as a synthetic lubricating oil is disclosed in JP-A-57-117.
No. 595. However, the obtained copolymer has a drawback that the molecular weight distribution is wide and cannot be put to practical use. Japanese Patent No. 2500262 discloses a liquid α-form having a narrow molecular weight distribution in order to improve the above-mentioned drawbacks.
Olefins have been proposed. It has a relatively high molecular weight.

[0012]

SUMMARY OF THE INVENTION The present invention relates to an ethylene / α-olefin copolymer useful as a resin modifier and a lubricating oil component, a method for producing the same, a resin composition containing the same, a molded article, and a lubricating oil. The purpose is to provide.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the triad chain distribution of ethylene and α-olefin and α-olefin measured by ¹³ C nuclear magnetic resonance spectrum. It has been found that an ethylene-based copolymer whose content satisfies a specific relational expression and whose intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is in a specific range can solve the above-mentioned problems, The present invention has been completed.

That is, the present invention provides the following ethylene copolymers, a method for producing the same, and a resin composition containing the same.
A molded article and a lubricating oil are provided. (1) triad sequence distribution of ¹³ ethylene measured by C nuclear magnetic resonance spectrum (E) and α- olefin (A) [EAE], [ EAA] and ¹³ are the α- olefin content measured by C nuclear magnetic resonance spectrum The amount α (mol%) is represented by the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and an ethylene copolymer satisfying the relationship of 1 ≦ α <55 and having an intrinsic viscosity [η] of 0.01 to 20 (dl / g) measured at 135 ° C. dissolved in decalin. (2) triad sequence distribution of ¹³ ethylene measured by C nuclear magnetic resonance spectrum (E) and α- olefin (A) [EAE], [ EAA] and ¹³ are the α- olefin content measured by C nuclear magnetic resonance spectrum The amount α (mol%) is represented by the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and the weight average molecular weight measured by gel permeation chromatography is 100 to 10
An ethylene-based copolymer which is 00000. (3) The diad chain distributions [EE], [AA] and [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum are expressed by the formula 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
An ethylene copolymer satisfying the relationship of 0.7 and having an intrinsic viscosity [η] of 0.01 to 20 (dl / g) measured at 135 ° C. dissolved in decalin. (4) The diad chain distributions [EE], [AA] and [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum are represented by the formula 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.7 and a weight average molecular weight of 100 to 10 as measured by gel permeation chromatography.
An ethylene-based copolymer which is 00000. (5) The ethylene copolymer according to any one of (1) to (4) above, wherein the α-olefin is either propylene or 1-butene. (6) Weight average molecular weight (Mw) and number average molecular weight (Mn)
The ethylene-based copolymer according to any one of the above 1 to 5, wherein the ratio (Mw / Mn) of the ethylene copolymer satisfies the relationship of 2.1 <Mw / Mn ≦ 4. (7) (A) The following general formula (I) or (II)

[0015]

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[0016]

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Wherein R ^{1 to} R ¹² and X ^{1 to} X ⁴ are
Each independently a hydrogen atom, a halogen atom, carbon number 1-2
A hydrocarbon group of 0, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. It may be formed. R ⁹ and R ¹⁰ may be the same or different. Y ^{1 to} Y ⁴ each independently represent a divalent group bonding two ligands, each having 1 carbon atom.
20 hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - NR ^{13
-, - PR 13 -, -} P (O) R 13 -, - BR 13 - or -AlR ¹³ - indicates, R ¹³ is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms are shown. M ¹ and M ² are the periodic table I
Shows transition metals of VA, VA and VIA groups. And (B) (a)
A catalyst for producing an olefin polymer, comprising an organoaluminum oxy compound and (b) at least one selected from ionic compounds capable of reacting with the transition metal compound to be converted to a cation. In the presence,
7. The method for producing an ethylene copolymer according to any one of the above 1 to 6, wherein ethylene and an α-olefin are copolymerized. (8) A thermoplastic resin composition containing the ethylene copolymer according to any one of the above (1) to (6). (9) A molded article obtained from the thermoplastic resin composition according to the above (8). (10) A lubricating oil containing the ethylene copolymer according to any one of (1) to (6) above.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to the above-mentioned ethylene copolymer, a method for producing the same, a resin composition containing the same, a molded product and a lubricating oil. The ethylene copolymer of the present invention is an ethylene / α-olefin copolymer having a specific structure (highly alternating) and a specific molecular weight range, and includes a resin modifier and a lubricating oil component. It is suitable as. The resin composition and the molded article containing the ethylene copolymer are excellent in flexibility, transparency, impact resistance, especially low-temperature impact resistance and mechanical strength, and lubricating oil is excellent in viscosity index and pour point.

Hereinafter, the present invention will be described in detail. 1. Ethylene-based copolymer The ethylene-based copolymer of the present invention has a triad chain distribution [EAE], [EAA] and ^{13C of} ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum. Α-olefin content α (mol%) measured by nuclear magnetic resonance spectrum
Is the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and has an intrinsic viscosity [η] of 0.01 to 20 (dl / g) measured at 135 ° C. dissolved in decalin (hereinafter referred to as ethylene of the first invention). System copolymer).

Further, the ethylene copolymer of the present invention has a triad chain distribution [EAE], [EAA] and ¹³ C of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum. Α-olefin content α (mol%) measured by nuclear magnetic resonance spectrum
Is the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and the weight average molecular weight measured by gel permeation chromatography is 100 to 10
00000 (hereinafter also referred to as the ethylene copolymer of the second invention).

Further, the ethylene copolymer of the present invention has a diad chain distribution [EE], [AA] and [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum. Is the formula 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.7, and the intrinsic viscosity [η] measured at 135 ° C. dissolved in decalin is 0.01 to 20 (dl / g) (hereinafter also referred to as the ethylene copolymer of the third invention). .

The ethylene copolymer of the present invention has a dyad chain distribution [EE], [AA] and [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum. Is the formula 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.7 and a weight average molecular weight of 100 to 10 as measured by gel permeation chromatography.
00000 (hereinafter also referred to as the ethylene copolymer of the fourth invention).

The ethylene copolymer of the present invention has the following formula: ([EAE] / [EAA]) / ((100-α) / α)
> 1.0 and 1 ≦ α <55, that is, the alternating between ethylene and α-olefin represented by micro-alternating from the relationship of the probability of the chain distribution of the monomer unit with respect to the composition ratio of the copolymer. Or a copolymer having a specific structure such that 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.7 which satisfies the relationship of 0.7, that is, the ethylene and α represented by the alternation from the relationship corresponding to the product of the monomer copolymerization reactivity ratios
-A copolymer having a specific structure in which olefin has a high alternating property. <Ethylene copolymer of the first invention> The ethylene copolymer of the present invention has a triad chain distribution [EAE] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum, Α-olefin content α (mol%) measured by [EAA] and ¹³ C nuclear magnetic resonance spectra
Is the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and the intrinsic viscosity [η] of 0.01 to 20 (dl / g) as measured by dissolving in decalin at 135 ° C.

As the α-olefin in the present invention,
Those having 3 to 20 carbon atoms are preferred, for example, propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene , 1-
Octadecene, 1-nonadecene, 1-eicosene and the like are mentioned, and one or more of these are used.
Among them, propylene, 1-butene, 1-hexene, 1-octene and the like, which are easily available and inexpensive, are more preferable, and propylene and 1-butene having a high copolymer yield are particularly preferable. Among them, 1-butene is most preferred.

The ethylene copolymer of the present invention has a triad chain distribution [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum.
E], [EAA] and the α-olefin content α (mol%) measured by ¹³ C nuclear magnetic resonance spectrum,
Formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0. If this relationship is not satisfied, the effect of improving the impact resistance at low temperatures will be small. From the viewpoint of this reforming effect, preferably, ([EAE] / [EAA]) / ((1−α) / α)>
1.2 More preferably, ([EAE] / [EAA]) / ((1-α) / α)>
1.4 Particularly preferably, ([EAE] / [EAA]) / ((1-α) / α)>
1.6.

The α-olefin content α in the present invention
(Mol%) is 1 mol% or more and 55 mol% or less. Preferably it is 10 mol% or more and 50 mol% or less. When the α-olefin content is 1 mol% or less, the compatibility with the polypropylene resin is poor, and the effect of modifying the resin is reduced. On the other hand, if the α-olefin content exceeds 55 mol%, the molecular mobility at low temperatures is low, so that the impact resistance at low temperatures is not exhibited when blended. The measurement method using the ¹³ C nuclear magnetic resonance spectrum will be described in detail in Examples.

Further, in addition to the above requirements, the ethylene copolymer of the present invention may have an intrinsic viscosity [η] of 0.01 to 20 (dl / g) when dissolved in decalin and measured at 135 ° C. is necessary. If [η] is less than 0.01 (dl / g), the stickiness component contained in the copolymer lowers the surface properties, and if it exceeds 20 (dl / g), the fluidity decreases. From these aspects, preferably 0.1 to 10 (d
1 / g), more preferably 0.1 to 5 (dl / g).
g).

The ethylene copolymer of the present invention has a ratio (Mw / Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of 2.1 <Mw / Mw measured by gel permeation chromatography. It is preferable to satisfy the relationship of Mn ≦ 4. More preferably, 2.1 <Mw / Mn ≦ 3.5, and particularly preferably, 2.1 <Mw / Mn ≦ 3. <Ethylene copolymer of the second invention> The ethylene copolymer of the present invention has a triad chain distribution [EAE] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum, Α-olefin content α (mol%) measured by [EAA] and ¹³ C nuclear magnetic resonance spectra
Is the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and the weight average molecular weight measured by gel permeation chromatography is 100 to 10
00000.

The contents described in the present invention are the same as those described for the ethylene copolymer of the first invention. It is necessary that the ethylene copolymer of the present invention satisfies the above condition, and that the weight average molecular weight measured by gel permeation chromatography is 100 to 1,000,000. If the weight average molecular weight is less than 100, the molecular weight is too low and the effect as a resin modifier or lubricating oil component cannot be obtained. If it exceeds 1,000,000, the effect as a resin modifier or lubricating oil component cannot be obtained.
From these aspects, it is preferably from 100 to 750000, and more preferably from 500 to 500,000. The measurement method by gel permeation chromatography will be described in detail in Examples.

As the α-olefin in the present invention,
The contents are the same as those described for the ethylene copolymer of the first invention. The Mw / Mn of the ethylene copolymer of the present invention measured by gel permeation chromatography is the same as that described for the ethylene copolymer of the first invention. <Ethylene copolymer of the third invention> The ethylene copolymer of the present invention has a diad chain distribution [EE] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum, [AA] and [EA] are represented by the formula 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.7, and the intrinsic viscosity [η] measured at 135 ° C. dissolved in decalin is 0.01 to 20 (dl / g).

4 × ([EE] × [AA]) / ([E
A]) When ² exceeds 0.7, the alternating copolymerizability of ethylene and α-olefin decreases, the molecular mobility at low temperature decreases, and the effect as a resin modifier or lubricating oil component is obtained. Not preferred. Preferably, 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.6 More preferably, 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.4 Particularly preferably, 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.2.

Further, in addition to the above requirements, the ethylene copolymer of the present invention may have a limiting viscosity [η] of 0.01 to 20 (dl / g) when dissolved in decalin and measured at 135 ° C. is necessary. If [η] is less than 0.01 (dl / g), the stickiness component contained in the copolymer lowers the surface properties, and if it exceeds 20 (dl / g), the fluidity decreases. From these aspects, preferably 0.1 to 10 (d
1 / g), more preferably 0.1 to 5 (dl / g).
g).

As the α-olefin in the present invention,
The contents are the same as those described for the ethylene copolymer of the first invention. The Mw / Mn of the ethylene copolymer of the present invention measured by gel permeation chromatography is the same as that described for the ethylene copolymer of the first invention. <Ethylene copolymer of the fourth invention> The ethylene copolymer of the present invention has a diad chain distribution [EE] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum, [AA] and [EA] are represented by the formula 0 <4 × ([EE] × [AA]) / ([EA]) ² ≦
0.7 and the weight average molecular weight measured by gel permeation chromatography is 100 to 100.
An ethylene-based copolymer which is 0000.

The contents of the present invention are the same as those described for the ethylene copolymer of the third invention. It is necessary that the ethylene copolymer of the present invention satisfies the above condition, and that the weight average molecular weight measured by gel permeation chromatography is 100 to 1,000,000. If the weight average molecular weight is less than 100, the molecular weight is too low and the effect as a resin modifier or lubricating oil component cannot be obtained. If it exceeds 1,000,000, the effect as a resin modifier or lubricating oil component cannot be obtained. From these aspects, preferably 100 to 7500
00, more preferably 500 to 500,000.

As the α-olefin in the present invention,
The contents are the same as those described for the ethylene copolymer of the first invention. The Mw / Mn of the ethylene copolymer of the present invention measured by gel permeation chromatography is the same as that described for the ethylene copolymer of the first invention. 2. Method for Producing Ethylene-Based Copolymer As a method for producing the ethylene-based copolymer of the present invention (the ethylene-based copolymer of the first to fourth inventions), ethylene and an α-olefin are used in the presence of a metallocene-based catalyst. Are copolymerized. Preferably, (A) a transition metal compound containing a transition metal belonging to Groups IVA, VA, and VIA of the periodic table, (B) (a) an organoaluminum oxy compound, and (b) a reaction with the above transition metal compound to convert to a cation. At least one selected from ionic compounds,
Further, this is a production method in which ethylene and an α-olefin are copolymerized in the presence of a catalyst containing, if necessary, an organometallic compound (C).

(A) Periodic Table IVA, VA, VIA
As the transition metal compound containing a group transition metal, a transition metal compound having a ligand containing two cycloalkadienyl skeletons cross-linked by one or more cross-linking groups is preferable,
Periodic table I represented by the following general formula (I) or (II)
Transition metal compounds of the VA, VA and VIA groups are more preferred. The crosslinking group is preferably an alkylene group, and the transition metal compound is preferably a meso-form or a C ₁ symmetric compound.

[0037]

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[0038]

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Wherein R ^{1 to} R ¹² and X ^{1 to} X ⁴ are
Each independently a hydrogen atom, a halogen atom, carbon number 1-2
A hydrocarbon group of 0, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. It may be formed. R ⁹ and R ¹⁰ may be the same or different. Y ^{1 to} Y ⁴ each independently represent a divalent group bonding two ligands, each having 1 carbon atom.
20 hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - NR ^{13
-, - PR 13 -, -} P (O) R 13 -, - BR 13 - or -AlR ¹³ - indicates, R ¹³ is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms are shown. M ¹ and M ² are the periodic table I
Shows transition metals of VA, VA and VIA groups. More specifically, as the compound represented by the general formula (I), a transition metal compound belonging to Group IVA, VA or VIA of the periodic table represented by the following general formula (I) A or (I) B is exemplified. be able to.

[0040]

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[0041]

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(Wherein R ^{14 to} R ³¹ and X ¹ and X ² are
Each independently a hydrogen atom, a halogen atom, carbon number 1-2
A hydrocarbon group of 0, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. It may be formed. Y ¹ and Y ² are each independently a divalent group bonding two ligands, each having 1 carbon atom.
20 hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - NR ^{32
-, - PR 32 -, -} P (O) R 32 -, - BR 32 - or -AlR ³² - are shown, R ³² is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms are shown. M ¹ is the periodic table IVA, V
A and VIA group transition metals are shown. Examples of the compound represented by the general formula (I) A include (1,1′-ethylene) (2,2′-ethylene) bisindenyl zirconium dichloride and (1,1′-ethylene) (2 , 2′-ethylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) bis (4-methylindenyl) zirconium dichloride, (1,1′- ethylene)
(2,2'-ethylene) bis (5-methylindenyl)
Zirconium dichloride, (1,1'-ethylene)
(2,2′-ethylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,1′-ethylene)
(2,2′-ethylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-ethylene)
(2,2′-ethylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1 ′ -Dimethylsilylene) (2,2′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1 ′
-Dimethylsilylene) (2,2'-dimethylsilylene)
Bis (4-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (5-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (4,5-benzoindenyl) Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene ) Bisindenyl zirconium dichloride, (1,1′-dimethylsilylene) (2,
2′-ethylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2'-ethylene) bis (4-methylindenyl)
Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) bis (5-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) bis ( 5,6-benzoindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) bis (4,5
-Benzoindenyl) zirconium dichloride, (1,
1′-dimethylsilylene) (2,2′-ethylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,
1′-ethylene) (2,2′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride,
(1,1′-ethylene) (2,2′-dimethylsilylene) bis (4-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) bis (5-methyl) (Indenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2 ′)
-Dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-ethylene)
Dichloro forms such as (2,2′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, and dimethyl, diethyl, dihydro, diphenyl, and dibenzyl forms of the above compounds, and titanium and hafnium thereof A complex can be illustrated.

Examples of the compound represented by the general formula (I) B include (1,1′-ethylene) (2,2′-ethylene) indenyl (3,5-dimethylcyclopentadienyl) zirconium dichloride. (1,1′-ethylene) (2,2′-ethylene) indenyl (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,1′-ethylene) (2,2′-ethylene) indenyl (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) (4-methylindene Nil) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-ethylene) (4-methylindenyl) (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) (5 -Methylindenyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (1,1'-ethylene) (2,
2′-ethylene) (5-methylindenyl) (3-methylcyclopentadienyl) dichloride such as zirconium dichloride and the like, and dimethyl, diethyl, dihydro, diphenyl and dibenzyl derivatives of the above Group 4 transition metal compounds And the like.

More specifically, the compound represented by the general formula (II) is represented by the following general formula (II) A or (I)
I) Transition metal compounds of groups IVA, VA and VIA of the periodic table represented by B.

[0045]

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[0046]

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Wherein R ^{33 to} R ⁵⁴ and X ³ and X ⁴ are
Each independently a hydrogen atom, a halogen atom, carbon number 1-2
A hydrocarbon group of 0, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. It may be formed. Y ³ and Y ⁴ are each independently a divalent group bonding two ligands, and each has 1 carbon atom.
20 hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - NR ^{55
-, - PR 55 -, -} P (O) R 55 -, - BR 55 - or -AlR ⁵⁵ - indicates, R ⁵⁵ is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms are shown. M ² is the Periodic Table IVA, V
A and VIA group transition metals are shown. Examples of the compound represented by the general formula (II) A include (1,1′-ethylene) (7,7′-ethylene) bisindenyl zirconium dichloride and (1,1′-ethylene) (7 , 7'-Ethylene) bis (2-methylindenyl) zirconium dichloride, (1,1'-ethylene) (7,7'-ethylene) bis (3-methylindenyl) zirconium dichloride, (1,1'- (Dimethylsilylene) (7,7'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-dimethylsilylene) (7,7'-dimethylsilylene) bis (2-methylindenyl) zirconium dichloride, 1'-dimethylsilylene) (7,7'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-ethylene) (7,7'-dimethylsilylene) bisindenyl zirconium dichloride, 1,1'-ethylene) (7,7'-dimethylsilylene) bis (2-methylindenyl) zirco Umujikurorido, (1,1'-ethylene) (7,7'
(Dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (7,7'-ethylene) bisindenylzirconium dichloride,
1'-dimethylsilylene) (7,7'-ethylene) bis (2-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (7,7'-ethylene) bis (3-methylindenyl) A dichloride such as zirconium dichloride;
Examples thereof include dimethyl, diethyl, dihydro, diphenyl, and dibenzyl compounds of the group III transition metal compound.

Examples of the compound represented by the general formula (II) B include (1,1′-ethylene) (2,7′-ethylene) (fluorenyl) (indenyl) zirconium dichloride,
(1,1'-ethylene) (2,7'-ethylene) (fluorenyl) (2-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-ethylene) (fluorenyl) (3 -Methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7 '
-Ethylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-ethylene) (9-methylfluorenyl) (indenyl) zirconium dichloride, (1,1 '-Ethylene) (2,7'-ethylene) (8-methylfluorenyl) (indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-ethylene) (fluorenyl) (indenyl) zirconium Dichloride, (1,1'-
Dimethylsilylene) (2,7'-ethylene) (fluorenyl) (2-
(Methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-ethylene) (fluorenyl) (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7 '-Ethylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-ethylene) (9-methylfluorenyl)
(Indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-ethylene) (8-methylfluorenyl) (indenyl) zirconium dichloride, (1,1'-ethylene) (2,7 ' -Dimethylsilylene) (fluorenyl) (indenyl) zirconium dichloride, (1,1'-ethylene) (2,7 '
-Dimethylsilylene) (fluorenyl) (2-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-
Dimethylsilylene) (fluorenyl) (3-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-
Dimethylsilylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-
Dimethylsilylene) (9-methylfluorenyl) (indenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-
Dimethylsilylene) (8-methylfluorenyl) (indenyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-dimethylsilylene) (fluorenyl) (indenyl)
Zirconium dichloride, (1,1'-dimethylsilyl) (2,
7'-dimethylsilylene) (fluorenyl) (2-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-dimethylsilylene) (fluorenyl) (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-dimethylsilylene)) (fluorenyl) (6-methylindenyl) Zirconium dichloride, (1,1'-dimethylsilyl) (2,7'-dimethylsilylene) (9-methylfluorenyl) (indenyl) zirconium dichloride, (1,1'-
Dimethylsilyl) (2,7′-dimethylsilylene) (8-methylfluorenyl) (indenyl) dichloride such as zirconium dichloride and dimethyl, diethyl, dihydro, diphenyl, dibenzyl of the above Group 4 transition metal compounds A body etc. can be illustrated.

The transition metal compound used as the component (A) may be used alone or in combination of two or more. The (a) organoaluminum oxy compound of the component (B) used in the present invention includes the following general formula (II)
I)

[0050]

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(Wherein, R ⁵⁶ represents an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, and n represents the degree of polymerization and is usually an integer of 2 to 50, preferably 2 to 40. Note that each R ⁵⁶ may be the same or different. Aluminoxane represented by the following general formula (IV):

[0052]

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(Wherein, R ⁵⁶ and n are the same as those described above). Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the method is not particularly limited, and the reaction may be performed according to a known method. For example, an organic aluminum compound is dissolved in an organic solvent,
A method in which this is brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and water is added later,
A method of reacting water of crystallization contained in metal salts or the like, water adsorbed on inorganic or organic substances with an organoaluminum compound,
There is a method in which a tetraalkyldialuminoxane is reacted with a trialkylaluminum and then with water. The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in a combination of two or more.

On the other hand, as the component (b), the component (A)
Which can react with the transition metal compound
Any compounds can be used as long as they are on compounds.
Is represented by the following general formulas (V) and (VI) ([L¹-R⁵⁷]^{k +})_a([Z]^-)_b ... (V) ([L^Two]^{k +})_a([Z]^-)_b ... (VI) (However, L^TwoIs M^Five, R⁵⁸R⁵⁹M⁶, R⁶⁰ _ThreeC or
R⁶¹M⁶It is. ) (In the formulas (V) and (VI), L¹Is a Lewis base, [Z]^-
Is a non-coordinating anion [Z¹]^-Or [Z^Two]^-This
Here [Z¹]^-Is an anion in which multiple groups are bonded to an element
That is, [M⁷G¹G^Two... G^f]^-(Where M⁷Is
Group 5 to 15 element of the periodic table, preferably 13 of the periodic table
Group 15 elements are shown. G¹~ G^fAre hydrogen atoms,
Halogen atom, alkyl group having 1 to 20 carbon atoms, 2 carbon atoms
Dialkylamino group having 1 to 40 carbon atoms and alcohol having 1 to 20 carbon atoms
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl aryl having 7 to 40 carbon atoms
Group, an arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
To 20 halogen-substituted hydrocarbon groups and 1 to 20 carbon atoms
Siloxy group, organic metalloid group or C2-20
Represents a hetero atom-containing hydrocarbon group. G¹~ G^fOut of
Two or more may form a ring. f is [(center metal M⁷
+1)]. ), [Z^Two] ^-Is acid digestion
The log of the reciprocal of the separation constant (pKa) is -10 or less.
Ted acid alone or Brønsted acid and Lewis acid
Combined conjugate bases, or generally defined as superacids
2 shows a conjugate base of an acid. In addition, Lewis base is coordinated.
You may. Also, R⁵⁷Is a hydrogen atom, an atom having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl ant
A aryl group or an arylalkyl group;⁵⁸And R
⁵⁹Is cyclopentadienyl group, substituted cyclopen
Tadienyl group, indenyl group or fluorenyl group, R⁶⁰
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
Indicates an aryl group or an arylalkyl group. R⁶¹Is
Macrocycles such as traphenylporphyrin and phthalocyanine
Shows a ligand. k is [L¹-R⁵⁷], [L^Two] Ion
Valence is an integer of 1 to 3, a is an integer of 1 or more, and b = (k ×
a). M ^FiveAre periodic table Nos. 1-3, 11-13,
Containing a Group 17 element,⁶Is the periodic table 7th
Shows Group 12 elements. ) Is preferably used.
Can be

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ⁵⁷ include hydrogen, methyl,
Examples of R ⁵⁸ and R ⁵⁹ include an ethyl group, a benzyl group, and a trityl group. Specific examples of R ⁵⁸ and R ⁵⁹ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentane. And a dienyl group. Specific examples of R ⁶⁰ include:
Phenyl, p- tolyl group, and a p- methoxyphenyl group, etc. Specific examples of R ^61, there can be mentioned tetraphenylporphyrin, phthalocyanine, allyl group, etc. methallyl group. Specific examples of M ⁵ include Li, Na, K, Ag, Cu, Br, I, and I.
_{3 and the} like. Specific examples of M ⁶ include M
n, Fe, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ⁷ G ¹ G
² ... G ^f ] ^- , as a specific example of M ⁷ ,
B, Al, Si, P, As, Sb and the like, preferably B and Al can be mentioned. In addition, G ^1, G ² ~G
Specific examples of ^f include a dimethylamino group, a diethylamino group, or the like as a dialkylamino group, a methoxy group, an ethoxy group, or an alkoxy group or an aryloxy group.
Examples of hydrocarbon groups such as n-butoxy group and phenoxy group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group,
Fluorine, chlorine, bromine, iodine, and hydrocarbons containing hetero atoms as halogen atoms such as n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, and 3,5-dimethylphenyl group Groups such as p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, Examples of the organic metalloid group such as a bis (trimethylsilyl) methyl group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group.

Further, a non-coordinating anion, ie, pK
a alone or Brensted acid having a of -10 or less
The conjugate base of the combination of Ted and Lewis acids [Z^Two]
^-As a specific example of trifluoromethanesulfonic acid
Neon (CF_ThreeSO_Three)^-, Bis (trifluoromethane
Sulfonyl) methyl anion, bis (trifluorometa)
Bisulfonyl) benzyl anion, bis (trifluoro
Methanesulfonyl) amide, perchlorate anion (ClO
_Four)^-, Trifluoroacetate anion (CF_ThreeCO
O)^-, Hexafluoroantimony anion (Sb
F₆)^-, Fluorosulfonic acid anion (FS
O_Three)^-, Chlorosulfonic acid anion (ClS
O_Three)^-, Fluorosulfonate anion / 5-fluoride
Nchimon (FSO_Three/ SbF_Five)^-, Fluorosulfone
Acid anion / 5-arsenic fluoride (FSO_Three/ As
F_Five)^-, Trifluoromethanesulfonic acid / 5-fluorinated
Antimony (CF_ThreeSO_Three/ SbF_Five) ^-Etc.
be able to.

Specific examples of the component (b) include triethylammonium tetraphenylborate,
Tri-n-butylammonium tetraphenylborate,
Trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate,
Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetraphenyl Benzylpyridinium borate, methyl tetraphenylborate (2-cyanopyridinium),
Triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, tri-tetrakis (pentafluorophenyl) borate Phenylammonium, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Methyldiphenylammonium fluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis ( Methylanilinium borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Benzylpyridinium borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium),
Benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), Triphenylphosphonium tetrakis (pentafluorophenyl) borate, Tetrakis [bis (3 5-
Ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate,
Manganese tetraphenylporphyrin tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
(1,1′-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis ( Lithium pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, Silver chlorate, silver trifluoroacetate,
Silver trifluoromethanesulfonate and the like can be mentioned.

The component (b) may be used alone or in combination of two or more. The proportion of the components (A) and (B) used in the production method of the present invention is as follows:
When the component (a) is used as the component (B), the molar ratio is preferably from 1: 1 to 1: 1,000,000, more preferably from 1:10 to 1: 10,000, and (b). When the components are used, the molar ratio is preferably 10: 1 to 1:
100, more preferably 2: 1 to 1:10. Further, as the component (B), (a) and (b) can be used alone or in combination of two or more.

In the present invention, the above-mentioned components (A) and (B) may be contained as main components, or the components (A), (B) and (C) It may contain a compound as a main component. Here, as the organoaluminum compound of the component (C), a general formula (VII) R ⁶² _v AlQ _3-v (VII) (wherein, R ⁶² is an alkyl group having 1 to 10 carbon atoms, and Q is hydrogen Atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Represents an aryl group or a halogen atom, and v is an integer of 1 to 3. ) Is used.

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and dimethylaluminum. Examples thereof include aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. The use ratio of the component (A) and the component (C) is preferably a molar ratio, preferably 1 :.
1-1: 10,000, more preferably 1: 5-1: 1:
2,000, more preferably 1:10 to 1: 1,000
0. By using the component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least the catalyst component
One can be used by supporting it on a suitable carrier. this
There is no particular limitation on the type of carrier, and
Body, other inorganic and organic carriers
Can be used, but there is nothing especially in terms of morphology control.
Organic oxide carriers or other inorganic carriers are preferred. Nothing
As the organic oxide carrier, specifically, SiO 2_Two, Al_Two
O_Three, MgO, ZrO_Two, TiO_Two, Fe_TwoO_Three, B_Two
O_Three, CaO, ZnO, BaO, ThO_TwoOr a mixture of these
Compounds such as silica alumina, zeolite, ferrai
And glass fiber. this
Among them, especially SiO_Two, Al_TwoO_ThreeIs preferred. What
In addition, the above inorganic oxide carrier contains a small amount of carbonate, nitrate, sulfuric acid.
It may contain an acid salt or the like. On the other hand, other carriers
And MgCl_Two, Mg (OC_TwoH _Five)_TwoMagnesi
General formula MgR represented by a compound such as⁶³ _XX^Five _yso
The magnesium compound represented and its complex salts are listed.
be able to. Where R ⁶³Is an alk having 1 to 20 carbon atoms
Group, an alkoxy group having 1 to 20 carbon atoms or 6 to 2 carbon atoms
An aryl group of 0, X^FiveIs a halogen atom or carbon number 1
20 represents an alkyl group, x is 0 to 2, y is 0 to 2
And x + y = 2. Each R⁶³And X ^FiveEach
They may be the same or different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Polypropylene, substituted polystyrene, polyarylate
Which polymer, starch, carbon, etc.
Wear. The carrier used in the present invention is MgC
l_Two, MgCl (OC_TwoH_Five), Mg (OC
_TwoH_Five) _Two, SiO_Two, Al_TwoO_ThreeAre preferred. Ma
The properties of the carrier differ depending on the type and manufacturing method,
The average particle size is usually 1 to 300 μm, preferably 10 to 20
0 μm, more preferably 20 to 100 μm. Particle size
When the particle size is small, fine powder in the polymer increases, and when the particle size is large,
Coarse particles in the coalescence increase, lowering the bulk density and clogging the hopper
It causes a ball. The specific surface area of the carrier is usually 1 to
1,000m^Two/ G, preferably 50 to 500 m^Two/
g, pore volume is usually 0.1-5cm^Three/ G, preferably
0.3-3cm^Three/ G. Specific surface area or pore volume
If any of the above deviates from the above range, the catalytic activity decreases.
Sometimes. The specific surface area and pore volume are, for example,
Calculated from the volume of nitrogen gas adsorbed according to the BET method
("J. Am. Chem. Soc.,60, 309 (1983) "
reference). Further, the carrier is usually 150 to 1,000.
C, preferably fired at 200-800C
Is desirable.

When at least one of the catalyst components is supported on the carrier, it is desirable to support at least one of the components (A) and (B), preferably both the components (A) and (B). The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, a method of mixing the carrier with at least one of the component (A) and the component (B). A method in which a carrier is treated with an organoaluminum compound or a halogen-containing silicon compound, and then mixed with at least one of the component (A) and the component (B) in an inert solvent, the carrier and the component (A) and / or (B) A method in which the component is reacted with an organoaluminum compound or a halogen-containing silicon compound, a method in which the component (A) or the component (B) is supported on a carrier, and then mixed with the component (B) or the component (A); A method of mixing the contact reactant of the component and the component (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the component (A) and the component (B) may be used. Can. In the above reaction,
An organoaluminum compound as the component (C) can be added.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, at least one of the components (A) and (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added,
A method in which an olefin such as ethylene is added at normal pressure to 20 kg / cm ^{2 and} prepolymerization is performed at −20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the weight ratio of the component (a) to the carrier is preferably 1: 0.5 to 1: 0.5.
The ratio is preferably 1: 1,000, more preferably 1: 1 to 1:50, and the use ratio of the component (b) to the carrier is preferably 1: 5 to 10,000, more preferably by weight. Is preferably 1:10 to 1: 500. When two or more catalyst components (B) are used as a mixture, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of the component (A) to the carrier is preferably in a weight ratio of 1: 5 to 1: 10,000.
0, more preferably 1:10 to 1: 500. If the ratio of the component (B) (component (a) or (b)) to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may be reduced. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 200 μm.
150 μm, particularly preferably 20 to 100 μm,
The specific surface area is usually 20~1,000m ² / g, preferably from 50 to 500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase,
If it exceeds μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1,000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the support is usually 0.05 to
It is preferably 10 g, particularly preferably 0.1 to 2 g. If the amount of the transition metal is out of the above range, the activity may be low. By supporting on a carrier in this manner, an industrially advantageous production method can be obtained.

The α-olefin in the production method of the present invention includes those having 3 to 20 carbon atoms.
For example, propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1- Eicosene, etc., and one or more of these are used. Among them, propylene, 1-butene, 1-hexene, 1-octene and the like, which are easily available and inexpensive, are preferable, and propylene and 1-butene having a high copolymer yield are more preferable. Among them, 1-butene is particularly preferred.

The molar ratio of ethylene and α-olefin used in the production is 0 <(ethylene / α-olefin)
It is preferred that ≦ 1. More preferably, 0 <(ethylene / α-olefin) ≦ 0.1. The copolymerization is
It may be carried out in the coexistence of ethylene and α-olefin. In the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Phase polymerization is particularly preferred. Regarding the polymerization conditions,
The polymerization temperature is usually -100 to 250C, preferably -50.
-200 ° C, more preferably 0-130 ° C. Further, the ratio of the catalyst to the reaction raw material is preferably such that the raw material monomer / the component (A) (molar ratio) is 1 to 10 ⁸ ,
It is particularly preferable to be 100 to 10 ^5. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 200 kg / cm ² G, particularly preferably normal pressure to 10 kg / cm ² G.
It is 0 kg / cm ² G. Methods for controlling the molecular weight of the polymer include selecting the type and amount of each catalyst component, selecting the polymerization temperature,
Further, there is polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in a combination of two or more. Further, a monomer such as propylene may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the present invention, preliminary polymerization can be performed using the polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited,
A known method can be used. There is no particular limitation on the olefin used for the prepolymerization, for example, ethylene,
Examples thereof include α-olefins having 3 to 20 carbon atoms, and mixtures thereof, and it is advantageous to use the same olefin as the monomer used in the polymerization. The pre-polymerization temperature is usually -20 to 200C, preferably -10 to 130C, more preferably 0 to 80C.
It is. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.1 deciliter / g or more, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1%. Up to 10,000
g, particularly preferably 10 to 1,000 g. Thus, the ethylene copolymer of the present invention can be efficiently obtained.

The molecular weight can be adjusted by adding a chain transfer agent, preferably by adding hydrogen.
An inert gas such as nitrogen may be present. 3. Resin composition The resin composition of the present invention is a thermoplastic resin composition containing the above-mentioned ethylene copolymer. The resin to be blended is not particularly limited, but it is preferable to use a polypropylene-based resin because of its low specific gravity and high rigidity.

As the polypropylene resin used in the present invention, those generally used can be used. For example, a propylene homopolymer, a propylene / ethylene block copolymer having an ethylene content of 20 to 70% by weight, a propylene / ethylene random copolymer having an ethylene content of 0.5 to 12% by weight, and an ethylene content of 0.5 to
For example, a propylene / ethylene / α-olefin terpolymer having an α-olefin content of 0.5 to 20% by weight, such as 12% by weight and butene-1, may be used. Alternatively, a crystalline polypropylene-based resin in which the stereoregularity of propylene has a syndiotactic structure may be used.

The blend ratio of the polypropylene resin (A) and the ethylene copolymer (B) is usually 5 to 70% by weight of the polypropylene resin (A) and 95 to 30% by weight of the ethylene copolymer (B). It can be arbitrarily changed according to the intended use and required physical properties. When the content of the polypropylene resin (A) exceeds 70% by weight, the flexibility of the composition becomes poor, and when it is less than 5% by weight, the strength is remarkably reduced, which is not preferable.

In the resin composition of the present invention, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericanite, zeolite,
Nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide,
Inorganic fillers such as graphite, gypsum, glass beads, glass powder, glass balloons, quartz, quartz glass, and organic,
Inorganic pigments can also be blended. In addition, crystal nucleating agents, clarifying agents, release agents, antistatic agents, slip agents, lubricants, heat stabilizers, weathering stabilizers, foaming agents, rust inhibitors, ion trap agents, flame retardants, flame retardant assistants May be added as necessary. In addition, the compositions of the present invention can be blended with other resins. In this case, a compatibilizing agent for the present resin composition and another resin can be used in combination as the third component.

The resin composition of the present invention can be obtained by blending a polypropylene resin and an ethylene copolymer by a commonly used method.
It is preferable to produce by melt blending using a roll, a Banbury mixer, an extruder or the like. 4. Molded body The molded body of the present invention can be formed by molding the above resin composition by any one of injection, compression, extrusion, vacuum, pressurized air and blow molding methods. The obtained molded product is flexible,
It becomes a transparent soft molded article having excellent transparency and impact resistance, especially low-temperature impact resistance. 5. Lubricating Oil The lubricating oil of the present invention contains 1.0 to 30.0% by weight, preferably 2.0% by weight of the above-mentioned ethylene copolymer as a component.
To 20.0% by weight, particularly preferably 2.0 to 15.0.
It is a lubricating oil containing by weight. The lubricating oil is not particularly limited, and is used for internal combustion engine oil such as gasoline engine oil (two-cycle, four-cycle), diesel engine oil, gear oil,
For drive system such as ATF, PSF, buffer oil and chassis oil,
Examples include equipment oils such as turbine oil, hydraulic oil, transmission oil, machine tool oil, and refrigerating machine oil, processing oils such as rolling oil, cutting grinding oil, heat treatment oil, and grease.

[0076]

Next, the present invention will be specifically described by way of examples.
The present invention is not limited at all by the following Examples. In addition, physical property evaluation was performed according to the following method. (1) Intrinsic viscosity [η] It was dissolved in decalin and measured at 135 ° C. (2) Sequence distribution [EE], [AA], [EA],
[EAE], [EAA] A polymer was dissolved in 1,2,4-trichlorobenzene, and proton complete decoupling was performed at 130 ° C. using ¹³ C-NMR (EX-400 manufactured by JEOL Ltd.). Quantification was performed using the signals of the methyl group, methylene group and methine group measured by the above.

[0077] Shi - cans distribution dyad sequence distribution used in the present invention as an index of the [EE], [AA] and triad sequence distribution [EAE], and [EAA], ¹³
C means the proportion of ethylene (E) and α-olefin (A) in two units and three units in the molecular chain of the ethylene copolymer measured by nuclear magnetic resonance spectroscopy. For example, [EE] indicates the ratio of ethylene to ethylene in a two-unit series.
The method for determining the assignment of peaks in the measurement of the ¹³ C nuclear magnetic resonance spectrum is described in HN Chen.
g) et al., according to the assignment proposed in "Macromolecules, 24 , 4813 (1991)". (3) alpha-olefin content [alpha] (mol%) of the polymer was dissolved in 1,2,4-trichlorobenzene, ¹³
Using C-NMR (EX-400 manufactured by JEOL Ltd.), quantification was performed using signals of a methyl group, a methylene group, and a methine group measured at 130 ° C. by a proton complete decoupling method. (4) Mw / Mn GPC-880 manufactured by JASCO (column: TSKG manufactured by Tosoh)
MH-6 × 1, GL-A120 × 1, made by Hitachi, GL
-A130 × 1) Using an apparatus, the solvent was chloroform, the temperature was 23 ° C., and the measurement was made in terms of polystyrene. (5) Impact resistance Izod impact strength at −30 ° C. was measured according to JIS K 7110. (6) Rigidity The tensile modulus was measured in accordance with JIS K6301. Example 1 (1) (1,1′-ethylene) (2,2′-ethylene)
Production of bisindenyl zirconium dichloride Production of 1,4-bis (phenylsulfonyl) butane Sodium benzenesulfinate 7 into a three-necked flask
5.0 g (457 mmol), 18.1 g of tetrabutylammonium bromide, 30 mL of benzene and 40 mL of water were added, and 22.5 mL (188 mmol) of 1,4-dibromobutane was added at room temperature.
Was added. After heating at 85 ° C. for 8 hours, the temperature was returned to room temperature, and 300 ml of ethyl acetate was added. Separate the organic layer,
After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure using an evaporator, and the obtained solid was recrystallized from methanol to obtain the desired product. The yield was 40.3 g and the yield was 63.0%. ¹ H-NMR (CDCl ₃ ) measurement of this compound gave the following results. 1.79 to 1.82 ppm (m, 4H), 3.05 pp
m (brt, J = 6.6 Hz, 4H), 7.52-7.
Production of 83 ppm (m, 10H) 1,2-bis (2-indenyl) ethane 16.9 g (50.0 mmol) of 1,4-bis (phenylsulfonyl) butane obtained in a three-necked flask, tetrahydrofuran 500 After dissolving in milliliters, the mixture was cooled to 0 ° C., and n-butyl lithium 1.6
128 ml of a mol / liter hexane solution (n-
(Butyllithium 205 mmol) was added dropwise. 1 after dripping
After stirring for an hour and further stirring vigorously, a solution of 17.9 g (102 mmol) of α, α'-dichloro-o-xylene in 500 ml of tetrahydrofuran was added dropwise,
Stirred at room temperature for 2 hours. The mixture was cooled to -78 ° C and n-butyllithium 1.6 mol / liter hexane solution 256
250 ml of a tetrahydrofuran solution of lithium diisopropylamide prepared from milliliter and 57.7 ml of diisopropylamine was gradually added dropwise. After stirring for 30 minutes, the mixture was cooled to 0 ° C. and 200 ml of 5% hydrochloric acid was added. Ethyl acetate 300 was added to the obtained reaction solution.
Milliliter was added. The organic layer was separated, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure using an evaporator.
The obtained solid was subjected to Soxhlet extraction using hexane to obtain the desired product. The yield was 2.0 g, and the yield was 15.0%. ¹ H-NMR (CDCl ₃ ) measurement of this compound gave the following results. 2.82 ppm (s, 4H), 3.36 ppm (s, 4H)
H), 6.57 ppm (s, 2H), 7.11-7.2.
Production of 8 ppm (m, 8H) (1,1′-ethylene) (2,2′-ethylene) bisindene 2.0 g of 1,2-bis (2-indenyl) ethane obtained in a three-necked flask (7 0.8 mmol) and 120 ml of tetrahydrofuran were added and dissolved, and then 0 ° C.
Then, 11.6 ml of a 1.6 mol / l hexane solution of n-butyllithium (18.6 mmol of n-butyllithium) was added dropwise. After the dropwise addition, the mixture was stirred for 30 minutes, 3.4 ml (15.6 mmol) of hexamethylphosphoramide was added, and the mixture was cooled to -78 ° C, and 0.76 ml of dibromoethane (7.7) was added.
Mmol). After stirring at room temperature for 3 hours, water was added, and 300 ml of ethyl acetate was further added.
The organic layer was separated, dried over anhydrous magnesium sulfate, concentrated under reduced pressure using an evaporator, and the obtained solid was recrystallized from hexane / methylene chloride (3/1) to obtain the desired product. The yield was 1.0 g and the yield was 45.0%. ¹ H-NMR (CDCl ₃ ) measurement of this compound gave the following results. 2.97 ppm (p, 4H), 3.05 ppm (p, 4H)
H), 3.27 ppm (s, 4H), 7.0-7.4 p.
pm (m, 8H) Production of (1,1′-ethylene) (2,2′-ethylene) bisindenyl zirconium dichloride (1,1′-ethylene) obtained in a three-necked flask
1.0 g of (2,2′-ethylene) bisindene (3.5
Mmol) and 80 ml of diethyl ether were dissolved therein, cooled to -78 ° C, and 4.8 ml of a 1.6 mol / l hexane solution of n-butyllithium (7.7 mmol of n-butyllithium) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature overnight, diethyl ether was distilled off under reduced pressure, and the obtained solid was washed with hexane. This solid was dissolved in 30 ml of toluene,
Was slowly added dropwise to a toluene suspension of 0.72 g (3.1 mmol) of zirconium tetrachloride which had been cooled. The obtained reaction solution was filtered, and the filtrate was concentrated under reduced pressure using an evaporator.
The obtained solid was recrystallized from hexane / toluene to obtain the desired product. The yield was 0.60 g, and the yield was 38.0%.
¹ H-NMR (CDCl ₃ ) measurement of this compound gave the following results. 3.50 ppm (d, 4H), 3.76 ppm (d, 4H)
H), 6.49 ppm (s, 2H), 6.90-7.5.
0 ppm (m, 8H) (2) Polymerization A 1-liter stainless steel autoclave with a stirrer having an internal volume of 1 liter was sufficiently dried, and after purging with nitrogen, 300 ml of 1-butene and 4.0 mmol of triisobutylaluminum were added. The temperature of the autoclave was raised to 50 ° C., and ethylene was introduced until the total pressure reached 5.2 kg / cm ² G. Subsequently, 1.0 mmol of triisobutylaluminum, 5 μmol of tetrakispentafluorophenylborate dimethylanilinium salt and (1,1′-ethylene) (2,2′-ethylene) prepared in (1).
Bisindenyl zirconium dichloride, 2.3 μmol of a mixed solution of 2.3 μmol of heptane, was charged to initiate polymerization. While supplying ethylene so that the total pressure becomes constant at 5.2 kg / cm ² G, 1
The polymerization was carried out for a time. Thereafter, the temperature was lowered and the pressure was released, and the contents were taken out and poured into 2 liters of methanol to obtain an ethylene copolymer. The results are shown in Table 1. (3) Evaluation 24 parts by weight of the ethylene copolymer obtained in (2) and polypropylene (IDEMITSU manufactured by Idemitsu Petrochemical Co., Ltd.)
PP J6083HP) 71 parts by weight and talc FFR (Asada Flour Milling Co., Ltd.) 5 parts by weight are mixed and melt-kneaded with a twin-screw extruder (Nippon Steel Works Co., Ltd. TEX-44) to obtain a propylene-based resin. A composition was obtained. A test piece was prepared from this composition by injection molding, and the physical properties were evaluated. First result
It is shown in the table. Example 2 The same operation as in Example 1 was performed except that ethylene was introduced until the total pressure reached 4.8 kg / cm ² G. The results are shown in Table 1. Example 3 (1) Synthesis of (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride 10.8 g of Mg (44) was placed in a three-necked flask purged with nitrogen.
4 mmol) and 45 ml of THF (tetrahydrofuran)
And 0.6 ml of 1,2-dibromomethane was added. After stirring for 5 minutes, the solvent was removed and THF 200
ml was added. α, α-dichloro-o-xylene
3 g (105 mmol) are dissolved in 300 ml of THF,
This solution was added dropwise at room temperature over 3 hours. The reaction mixture was further stirred at room temperature for 15 hours. The reaction mixture was cooled to -78 ° C.
And cooled to 6.6 g of dimethylmalonic acid diethyl ester
(36.2 mmol) in 100 ml of THF was added dropwise over 1 hour. After stirring at room temperature for another 2 hours, water 100
ml was added. The reaction mixture was subjected to suction filtration, the solvent of the filtrate was distilled off under reduced pressure, and then a 1N aqueous ammonium chloride solution was added, followed by extraction with dichloromethane. The organic phase is extracted with 100 ml of water 2
After washing twice, it was dried over anhydrous magnesium sulfate. Evaporation of the solvent gave a yellow oil. The compound (1) was further purified by column chromatography and recrystallized from hexane to give compound (1) as colorless crystals (4.8).
g (44% yield). When the ¹ H-NMR of this product was determined, the following results were obtained.

¹ H-NMR (CDCl ₃ ) δ: 1.235 (s, 6
H, CH ₃ ), 3.002 (d, J = 16.4Hz), and 3.470 (d, J = 16.4 H
z) (8H, CH ₂ ), 3.767 (s, 2H, OH), 7.2-7.4 (m, 8H, PhH)

[0079]

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(Me represents a methyl group; the same applies hereinafter) Compound (1) (4.8 g, 15.9 mmol) was dissolved in dichloromethane (30 ml), and p-toluenesulfonic acid (3.04 g, (15.9 mmol) was added thereto). The reaction mixture was washed with an aqueous sodium hydrogen carbonate solution and then with water, and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure to obtain a yellow oil. The compound (2) was purified by silica gel column chromatography and recrystallized from hexane to give compound (2) in 2.3.
g (54% yield). When the ¹ H-NMR of this product was determined, the following results were obtained.

¹ H-NMR (CDCl ₃ ) δ: 1.586 (s,
6H, CH ₃ ), 3.470 (s, 4H, CH ₂ ), 3.767 (s, 2H, CpH),
6.9-7.5 (m, 8H, PhH)

[0082]

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To a Schlenk tube purged with nitrogen, 6.2 g (22.7 mmol) of compound (2) and 50 ml of diethyl ether were added. The solution was cooled to -78 ° C and n-
28.4 ml of butyllithium (1.60 mol / l)
(45.4 mmol) was added dropwise. After stirring at room temperature for 3 hours,
The supernatant was removed and the precipitate was washed twice with 20 ml of diethyl ether. By drying under reduced pressure, the dilithium salt (3) was obtained as a white powder.

[0084]

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The dilithium salt (3) was added to THF 100 ml.
And dichlorodimethylsilane (3.0 g, 2
2.7 mmol) were added dropwise at room temperature. After stirring at room temperature for 3 hours, the solvent was distilled off, and 100 ml of water was added. The aqueous phase was extracted with 200 ml of dichloromethane and the organic phase was washed twice with water. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained solid was recrystallized from hexane to obtain 6.5 g of (4) as colorless crystals (yield 886.5%).
When the ¹ H-NMR of this product was determined, the following results were obtained.

¹ H-NMR (CDCl ₃ ) δ: -0.354 (s,
6H, SiCH ₃ ), 1.608 (s, 6H, CCH ₃ ), 3.347 (s, 2H, SiC
H), 6.785 (s, 2H, CpH), 6.9-7.6 (m, 8H, PhH)

[0087]

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In a Schlenk tube purged with nitrogen, 0.9 g (2.7 mmol) of compound (4) and 50 ml of hexane
Was added. The solution was cooled to 0 ° C., and 3.4 ml (5.4 mmol) of n-butyllithium (1.60 mol / l) was added.
l) It was added dropwise. After stirring at room temperature for 3 hours, the supernatant was removed, and the precipitate was washed twice with 50 ml of hexane. The solid was dried under reduced pressure to obtain the dilithium salt (5) as a pink powder.

[0089]

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50 ml of toluene was added to the dilithium salt (5).
Was added. To this suspension was added zirconium tetrachloride 0.63.
g (2.7 mmol) in 20 ml of toluene at 0 ° C.
Was dropped. After stirring at room temperature for 24 hours, the precipitate was removed by filtration, and the filtrate was concentrated. By recrystallization from toluene / hexane, 0.26 of (6) was obtained as yellow-orange crystals.
g (19% yield). When the ¹ H-NMR of this product was determined, the following results were obtained.

¹ H-NMR (CDCl ₃ ) δ: -0.172 (s,
3H, SiCH ₃ ), 0.749 (s, 3H, SiCH ₃ ), 1.346 (s, 3H, CC
H ₃ ), 2.141 (s, 3H, CCH ₃ ), 6.692 (s, 2H, CpH), 6.9-8.
1 (m, 8H, PhH)

[0092]

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(2) Polymerization 1-liter stainless steel autoclave
300 ml of butene, methylaluminoxane 10
After charging mmol, 2 kg / cm ² G of hydrogen was introduced, and the temperature was raised to 50 ° C. Here, ethylene gas was introduced, 1 mmol of isobutylaluminum, and
A mixed solution of 10 μmol of (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride was charged. During polymerization
Ethylene was continuously supplied at 0.2 l / min. 30
After a minute, the content was taken out and dried under reduced pressure to obtain an ethylene copolymer. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1. [Example 4] The copolymer obtained in Example 3 was subjected to JI
The pour point is determined according to JIS K2269
The viscosity and the viscosity index were measured according to 283. As a result, the pour point was −32.5 ° C., the kinematic viscosity at 100 ° C. was 93.28 mm ² / s, and the kinematic viscosity at 40 ° C. was 1
206 mm ² / s, viscosity index was 162. Comparative Example 1 (1) (1,2′-ethylene) (2,1′-ethylene)
-Production of bis (indenyl) zirconium dichloride Production of ethyl (2-indenyl) acetate 3.3 g (0.14 mol) of sodium hydride was suspended in 300 ml of tetrahydrofuran under a nitrogen stream and cooled to 10 ° C. To this suspension, 200 ml of a tetrahydrofuran solution of 28.3 g (0.11 mol) of ethyl diethylphosphonoacetate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes and cooled with ice, and thereto was added dropwise a solution of 16.33 g (0.12 mol) of 2-indanone in 75 ml of tetrahydrofuran over 1 hour. After dropping, the mixture was stirred at room temperature for 30 minutes,
After hydrolysis with water, extraction was performed with 500 ml of diethyl ether, and the organic layer was separated. After that, the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to isolate ethyl (2-indenyl) acetate as a pale yellow oil. The amount was 11.06 g, and the yield was 49.5%. ¹ H-NMR (CDCl ₃ ) measurement of this compound gave the following results. 1.23 ppm (t, 3H), 3.40 ppm (s, 2
H), 3.45 ppm (s, 2H), 4.16 ppm
(Q, 2H), 6.65 ppm (s, 1H), 6.94
-7.50 ppm (m, 4H) Production of 2- (2-indenyl) -ethanol 2.2 g of lithium aluminum hydride (5
(8.49 mmol) in 100 ml of diethyl ether. To this suspension was added 11 g of ethyl (2-indenyl) acetate obtained above (59.06).
(Mmol) of diethyl ether was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, cooled on ice, 50 ml of water was gradually added, and dilute hydrochloric acid was further added to dissolve insolubles. The organic layer was separated, and the solvent was distilled off under reduced pressure to obtain 2- (2-indenyl) -ethanol as a white solid. The yield was 7.89 g. This was used for the next reaction without further purification. ¹ H-NMR (CDCl ₃ ) measurement of this compound gave the following results. 1.56 ppm (s, 1H), 2.76 ppm (t, 2
H), 3.37 ppm (s, 2H), 3.83 ppm
(T, 2H), 6.62 ppm (s, 1H), 6.95
-7.62 ppm (m, 4H) Production of 1-bromo-2- (2-indenyl) ethane 2- (2-indenyl) obtained above under a nitrogen stream.
4.61 g (28.77 mmol) of ethanol were dissolved in 65 ml of dichloromethane. After adding 7.66 g (29.20 mmol) of triphenylphosphine to this solution, N-bromosuccinimide 5.19 was added.
g (29.16 mmol) was added slowly. After the addition of N-bromosuccinimide was completed, the mixture was stirred at room temperature for 30 minutes, water was added thereto and stirred, then the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (developing solvent: hexane) to obtain 1-bromo-2- (2-indenyl) ethane as a colorless oil. Yield 5.07 g, Yield 8
0.85%. This compound was analyzed by ¹ H-NMR (CD
Cl ₃ ) was measured and was as follows. 3.02 ppm (t, 2H), 3.32 ppm (s, 2
H), 3.52 ppm (t, 2H), 6.60 ppm
(S, 1H), 6.93 to 7.53 ppm (m, 4H) Production of (1,2′-ethylene) (2,1′-ethylene) -bis (indene) Under a nitrogen stream, to 50 ml of tetrahydrofuran,
6.87 ml of diisopropylamine (52.4
(1 mmol) and cooled to -78 ° C. To this solution, 31.96 ml of a hexane solution having a concentration of n-butyllithium of 1.64 mol / liter (52.41 mmol of n-butyllithium) was added dropwise over 10 minutes. After the completion of the dropwise addition, the reaction mixture was naturally heated to 0 ° C. to prepare a lithium diisopropylamide solution.

Next, tetrahydrofuran 5
1-bromo-2- obtained above in 00 ml
After adding 11.69 g (52.39 mmol) of (2-indenyl) ethane and stirring and dissolving, the mixture was cooled to -78 ° C. Next, the lithium diisopropylamide solution prepared above was cooled to −78 ° C. and added dropwise to the solution over 30 minutes. After the completion of the dropwise addition of the lithium diisopropylamide solution, the temperature is allowed to naturally rise to room temperature, and then
Stirring was performed for 2 hours. After adding 500 ml of water to the reaction mixture and washing the organic layer, anhydrous magnesium sulfate was added to dry the organic layer. After magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. As a white solid, (1,2′-ethylene) (2,1′-ethylene)-
5.95 g of a crude bis (indene) product was obtained. The crude product was analyzed by FD-MS (Field Desorption Mass Spectroscopy) to find that the desired product (1,2′-ethylene) (2,1′-ethylene) -bis (indene) (2 Monomer). This crude product is purified by sublimation at 0.2 Torr and 150 ° C. to give (1,2′-ethylene) (2,1′-ethylene)-
1.87 g of bis (indene) were obtained. The yield was 25.1%.

The structure of the compound was determined by FD-MS and ¹ H
-Confirmed by NMR. The FD-MS measurement was performed at an acceleration voltage of 8 kV. ¹ H-NMR (CDCl ₃ ): 3.02 ppm (s, 8
H), 3.29 ppm (s, 4H), 7.0-7.5p
pm (m, 8H) FD-MS: M ⁺ = 284 Production of dilithium salt of (1,2′-ethylene) (2,1′-ethylene) -bis (indene) Obtained above under a stream of nitrogen ( 1,2'-ethylene)
1.87 g of (2,1′-ethylene) -bis (indene)
(6.58 mmol) was added with 100 ml of diethyl ether, stirred and cooled to -78 ° C. To this, 8.02 ml of a hexane solution having a concentration of 1.64 mol / l of n-butyllithium (13.15 mmol of n-butyllithium) was added dropwise over 30 minutes. After the reaction mixture was naturally warmed to room temperature and stirred at room temperature for 12 hours, the reaction mixture was treated under reduced pressure to remove the solvent, and the residue was washed twice with 50 ml of hexane. By drying under reduced pressure, (1,
The dilithium salt of 2′-ethylene) (2,1′-ethylene) -bis (indene) was obtained as a pale yellow powder. The ¹ H-NMR of this product was determined, and the following results were obtained. This product was a diethyl ether adduct and was used in the next reaction. The yield was 1.63 g and the yield was 69.3%. ¹ H-NMR (THF-d ₈ ) measurement of this compound gave the following results. 3.22 ppm (8H), 5.38 ppm (s, 2
H), 5.95-6.35 ppm (m, 4H), 6.7.
Production of 0 to 7.20 ppm (m, 4H) (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride The above-obtained (1,2′-) obtained under a nitrogen stream. ethylene)
1.63 g (4.56 mmol) of a dilithium salt of (2,1′-ethylene) -bis (indene) was suspended in 50 ml of toluene and then cooled to −78 ° C. On the other hand, 1.06 g of zirconium tetrachloride (4.
(56 mmol) was suspended in 100 ml of toluene and then cooled to -78 ° C. To this zirconium tetrachloride toluene suspension, the previously prepared toluene suspension of (1,2′-ethylene) (2,1′-ethylene) -bis (indene) dilithium salt was added dropwise over 30 minutes. The reaction mixture was allowed to naturally warm to room temperature, stirred at room temperature for 12 hours, filtered off the toluene supernatant, and extracted twice with 50 ml of dichloromethane.

After distilling off the solvent under reduced pressure, the residue was distilled.
By recrystallization from dichloromethane / hexane, (1,
2'-ethylene) (2,1'-ethylene) -bis (in
0.25 g of (denyl) zirconium dichloride was obtained. Income
Rate was 12.3%. This compound¹H-NMR (C
DCI_Three) Measurements were as follows. 3.62 ppm (8H), 6.53 ppm (s, 2
H), 6.90-7.60 ppm (m, 8H) (2) Polymerization 1 liter stainless steel autoclave with stirrer
After drying thoroughly, replacing with nitrogen, 45 g of 1-butene and
And 1.0 mmol of triisobutylaluminum
Was. 5. The autoclave temperature was raised to 50 ° C and the total pressure was 6.
0kg / cm^TwoEthylene was introduced until G was reached. Continued
1.0 mmol of triisobutylaluminum, tetra
Kispentafluorophenylborate dimethylanilini
Prepared in (1)
2'-ethylene) (2,1'-ethylene) bisindene
Ruzirconium dichloride 2.5 micromolar hepta
Polymerization was started by adding 2.5 ml of the mixed solution
Was. Total pressure is 6.0kg / cm ^TwoTo be constant at G
Polymerization at a temperature of 50 ° C for 30 hours while supplying ethylene
Was carried out. Thereafter, the temperature is lowered and the pressure is released, and the contents are taken out.
After pouring into liter of methanol, ethylene copolymer
I got The results are shown in Table 1. (3) Evaluation The same operation as in Example 1 (3) was performed. Table 1 shows the results
Show.

[0097]

[Table 1]

[0098]

The ethylene copolymer of the present invention is useful as a resin modifier and a lubricating oil component. The resin composition containing the ethylene copolymer of the present invention gives a molded article excellent in flexibility, transparency and impact resistance, especially low-temperature impact resistance and mechanical strength. Further, a lubricating oil having an excellent viscosity index and pour point can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C10N 30:02

Claims (10)

[Claims] (1)¹³Measured by C nuclear magnetic resonance spectrum
Of ethylene (E) and α-olefin (A)
Chain distributions [EAE], [EAA] and ¹³C nuclear magnetism
Α-Olefin content measured by resonance spectrum
α (mol%) is represented by the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and dissolved in decalin and measured at 135 ° C.
When the intrinsic viscosity [η] is 0.01 to 20 (dl / g)
An ethylene copolymer. (2)¹³Measured by C nuclear magnetic resonance spectrum
Of ethylene (E) and α-olefin (A)
Chain distributions [EAE], [EAA] and ¹³C nuclear magnetism
Α-Olefin content measured by resonance spectrum
α (mol%) is represented by the formula ([EAE] / [EAA]) / ((100−α) / α)
> 1.0 and 1 ≦ α <55, and gel permeation chromatography
Weight average molecular weight of 100 to 10
An ethylene-based copolymer which is 00000. 3. The diad chain distributions [EE], [AA] and [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum are represented by the formula 0 <4 × ([ EE] × [AA]) / ([EA]) ² ≦
An ethylene copolymer satisfying the relationship of 0.7 and having an intrinsic viscosity [η] of 0.01 to 20 (dl / g) measured at 135 ° C. dissolved in decalin. 4. The diad chain distributions [EE], [AA] and [EA] of ethylene (E) and α-olefin (A) measured by ¹³ C nuclear magnetic resonance spectrum are represented by the formula 0 <4 × ([ EE] × [AA]) / ([EA]) ² ≦
0.7 and a weight average molecular weight of 100 to 10 as measured by gel permeation chromatography.
An ethylene-based copolymer which is 00000. 5. The method according to claim 1, wherein the α-olefin is propylene or 1-olefin.
The ethylene copolymer according to any one of claims 1 to 4, which is any one of butene. 6. The method according to claim 1, wherein a ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) satisfies a relationship of 2.1 <Mw / Mn ≦ 4. Ethylene copolymer. (A) The following general formula (I) or (II): Embedded image (Wherein, R ^{1 to} R ¹² and X ^{1 to} X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing 1 to 20 carbon atoms, and a silicon-containing group. A group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, which may be bonded to an adjacent group to form a ring, wherein R ⁹ and R ¹⁰ are the same or different. Y ^{1 to} Y ⁴ are each independently a divalent group bonding two ligands, and each include a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, Silicon-containing groups, germanium-containing groups, tin-containing groups, -O-,
-CO -, - S -, - SO 2 -, - NR 13 -, - PR 13
-, - P (O) R 13 -, - BR 13 - or -AlR ¹³ -
Wherein R ¹³ is a hydrogen atom, a halogen atom, and having 1 to 2 carbon atoms.
0 represents a hydrocarbon group and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. M ¹ and M ² are the periodic tables IVA, VA,
5 shows a VIA group transition metal. And at least one selected from (B) (a) an organoaluminum oxy compound and (b) an ionic compound capable of reacting with the transition metal compound to convert it to a cation. Ethylene and α in the presence of an olefin polymer production catalyst characterized by comprising
The method for producing an ethylene copolymer according to any one of claims 1 to 6, wherein the olefin is copolymerized. 8. A thermoplastic resin composition containing the ethylene copolymer according to claim 1. 9. A molded article obtained from the thermoplastic resin composition according to claim 8. 10. A lubricating oil comprising the ethylene copolymer according to claim 1.