JP2004197081A - Foamed article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a foamed article excellent in balance between remaining compressive stress rate which is an indicator of a shape retaining property, and BIT which is an indicator of kneading property. <P>SOLUTION: The foamed articles are obtained by using an ethylene-alpha-olefin-non-conjugated diene copolymer rubber satisfying following requirements (1) to (4): (1) a ratio of a Z-average molecular chain length (Az) measured according to a gel permeation chromatography to a number average molecular chain length (An), Az/An, of the ethylene-alpha-olefin-non-conjugated diene copolymer rubber is from 20 to 30, (2) a ratio of a weight average molecular chain length (Aw) to the number average molecular chain length (An), Aw/An, which is an index of a molecular weight distribution, of the ethylene-alpha-olefin-non-conjugated diene copolymer rubber is more than 5, (3) a unimodal or bimodal molecular weight distribution structure, which is present in a maximum amount in a range of 3.8<Log Aw<4.5, exists in the ethylene-alpha-olefin-non-conjugated diene copolymer rubber, and (4) a viscosity (ML<SB>1+4</SB>, 121°C.) of the ethylene-alpha-olefin-non-conjugated diene copolymer rubber measured with an ML viscometer is more than 60 and less than 160. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a foam obtained by using an ethylene-α-olefin-nonconjugated diene copolymer rubber excellent in specific kneading processability and shape retention.

  Ethylene-α-olefin-non-conjugated diene copolymer rubber has excellent properties such as heat resistance, weather resistance, and ozone resistance, and is used as a material for automobiles, building materials, industrial materials, electric wires, etc. It is widely used, especially in large quantities as window frame rubber for automobiles.

  However, these materials are intensifying in cost competition, so that the processing steps are rationalized and shortened in time. On the other hand, the thickness of the extruded product is becoming thinner in accordance with the demand for lower density of the foamed product. In the case of an olefin-non-conjugated diene copolymer rubber, if the molecular weight distribution is narrowed or the molecular weight is reduced for shortening the kneading time, shape retention characteristics are particularly deteriorated in the extrusion process, and a required shape may not be obtained. Conversely, if the molecular weight distribution is increased or the molecular weight is increased in order to improve the shape retention characteristics, the time required for kneading becomes longer or the extruded material surface deteriorates due to insufficient kneading, and the conventional ethylene-α -Foam using ethylene-α-olefin-non-conjugated diene copolymer rubber excellent in shape retention characteristics and capable of short-time kneading with improved kneading processability and shape retention balance of olefin-non-conjugated diene copolymer rubber Was required.

To meet such needs, proposals have been made to improve the balance by giving a branch using a narrow molecular weight distribution structure and a special diene component as the fourth component. (See Patent Document 1)
JP 2002-507228 A

  Under these circumstances, the problem to be solved by the present invention is to provide an ethylene-α-olefin-non-conjugated diene copolymer rubber having an excellent balance between kneading processability and shape retention characteristics of an extruded product by precisely controlling the molecular weight distribution. To provide a foam using the same.

That is, in the present invention, the ratio Az / An between the Z-average molecular chain length (Az) and the number average molecular chain length (An) measured by gel permeation chromatography (GPC) is in the range of 20 to 30. And the ratio Aw / An of the weight average molecular chain length (Aw) to An, which is an index of the molecular weight distribution, is greater than 5 and has a peak in the range of 3.8 <Log Aw <4.5. Or foam obtained by using an ethylene-α-olefin-non-conjugated diene copolymer rubber having a bimodal molecular weight distribution structure and a viscosity measured by an ML viscometer in the range of 60 <ML _{1 + 4} , 121 ° C. <160. It concerns the body.

  According to the present invention, by using a specific ethylene-α-olefin-non-conjugated diene copolymer rubber, a foam having an excellent balance between a residual compressive stress rate as an index of shape retention properties and a BIT as an index of kneading properties is obtained. The obtained foam was shown to have properties equivalent to those of a foam obtained using a conventional ethylene-α-olefin-nonconjugated diene copolymer rubber.

  The Z-average molecular chain length (Az) and the number-average molecular chain length (An) of the ethylene-α-olefin-non-conjugated diene copolymer rubber used in the present invention measured by gel permeation chromatography (GPC). The ratio Az / An is in the range of 20 to 30, and the ratio Aw / An of the weight average molecular chain length (Aw), which is an index of the molecular weight distribution, to An is greater than 5.

Z-average molecular chain length (Az), number average molecular chain length (An), and weight average molecular chain length (Aw) are generally represented by the following formula.
Z-average molecular chain length (Az) = ΣMp ³ · Np / ΣMp ² · Np
Number average molecular chain length (An) = ΣMp · Np / ΣNp
Weight average molecular chain length (Aw) = ΣMp ² · Np / ΣMp · Np
Here, Mp represents the molecular chain length of the molecular species having the degree of polymerization p in the polymer, and Np represents the number of molecules of the molecular species having the degree of polymerization p. As can be understood from the equation, the influence of the molecule having the larger molecular weight becomes stronger in the order of An, Aw, Az. That is, Az strongly reflects the influence of high molecular weight components in the polymer, and An strongly reflects the effect of low molecular weight components in the polymer.

  While the ratio Az / An between the Z-average molecular chain length (Az) and the number average molecular chain length (An) is defined in the range of 20 to 30, the weight average molecular chain length (Aw), which is an index of molecular weight distribution, and An When the ratio Aw / An is greater than 5, it means that the copolymer has a high molecular weight component and a low molecular weight component while controlling the content of the very high molecular weight component and the content of the very low molecular weight component. Indicates that.

In the ethylene-α-olefin-non-conjugated diene copolymer rubber used in the present invention, the molecular chain length component having the highest abundance measured by gel permeation chromatography (GPC) is 3.8 <Log Aw <4. 5, having a monomodal or bimodal molecular weight distribution structure, and having a viscosity measured by an ML viscometer in the range of 60 <ML _{1 + 4} , 121 ° C. <160 is a regulated ML viscosity. Since the molecular chain length component having the highest abundance in the range is defined to have a relatively high molecular weight, it means that it has a so-called trapezoidal molecular weight distribution.

  From these descriptions, the ethylene-α-olefin-non-conjugated diene copolymer rubber shown in the present invention has a unique molecular weight distribution structure. It is clear that this is suitable for the purpose of providing a foam using an ethylene-α-olefin-non-conjugated diene copolymer rubber which has an excellent balance of the shape-retaining properties of the molded article and which has excellent shape-retaining properties in a short time. Was.

More specifically, the ratio Az / An between the Z-average molecular chain length (Az) and the number average molecular chain length (An) measured by gel permeation chromatography (GPC) is in the range of 20 to 30, In addition, the ratio Aw / An of the weight average molecular chain length (Aw) to An, which is an index of the molecular weight distribution, is greater than 5, and a single peak having a peak in the range of 3.8 <Log Aw <4.5 or The present invention relates to an ethylene-α-olefin-nonconjugated diene copolymer rubber having a bimodal molecular weight distribution structure and having a viscosity measured by an ML viscometer in the range of 60 <ML _{1 + 4} , 121 ° C. <160. If Log Aw of the molecular chain length component having the highest abundance ratio is less than 3.8 while satisfying other conditions, the kneading time is prolonged, and if it is more than 4.5, the ethylene-α-olefin-non- Production of conjugated diene copolymer rubber becomes difficult.

When the viscosity ML _{1 + 4} , measured by an ML viscometer, at 121 ° C. is smaller than 60, generally there is little problem in kneading workability, and the effect of improving the balance between kneading and shape retention properties, which is the object of this patent, is not obtained. When it is larger than 160, it becomes difficult to produce an ethylene-α-olefin-non-conjugated diene copolymer rubber while satisfying the requirements of this patent.

  As the α-olefin of the ethylene-α-olefin-non-conjugated diene copolymer rubber specified by the present invention, an α-olefin having 3 to 20 carbon atoms is preferable, and two or more α-olefins can be used at the same time. Specific examples of the α-olefin include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene; Examples thereof include branched olefins such as 1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene, and vinylcyclohexane. Preferred are propylene and 1-butene, and particularly preferred is propylene.

  The weight ratio of ethylene units to α-olefin units in the copolymer rubber is preferably in the range of 80/20 to 45/55, and more preferably in the range of 50/50 to 70/30. When the content of the ethylene unit is larger than this, the flexibility as a rubber becomes poor, and the low-temperature properties of the obtained foam deteriorate. If the amount is less than this, an ethylene-α-olefin-non-conjugated diene copolymer rubber having a low molecular weight during polymerization and having essentially poor shape retention cannot be obtained, and a desired foam cannot be obtained.

As the non-conjugated diene in the ethylene-α-olefin-non-conjugated diene copolymer rubber defined by the present invention, a linear or cyclic non-conjugated diene or non-conjugated polyene monomer can be used. 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1,8 -Decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1 , 4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, dicyclo Antadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2, 5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7- Methylethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene , 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1 -Propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene, 1-bromo-2,5-norbornadiene and the like can be mentioned. Further, a cyclic diene having the following structure is also included.

  Among these, particularly preferred non-conjugated dienes include 5-ethylidene-2-norbornene alone or 5-ethylidene-2-norbornene and dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinylnorbornene, and 5-ethylidene- Examples include a combination of 2-norbornene and norbornadiene.

  The content of the non-conjugated diene in the ethylene-α-olefin-non-conjugated diene copolymer rubber defined by the present invention is in the range of 5 to 35 in terms of iodine value, particularly preferably 10 to 30, and more preferably 12 to 30. It is in the range of 25. When the content of the non-conjugated diene is lower than this, the crosslink density of the vulcanized rubber decreases, and the physical properties of the foam product, particularly the compression set, deteriorate. Conversely, if the content of the non-conjugated diene is too high, not only may the weather resistance deteriorate, but also the amount of expensive diene used increases, which is uneconomical.

In the case of a combination of 5-ethylidene-2-norbornene and dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinylnorbornene, and 5-ethylidene-2-norbornene and norbornadiene, the former and the latter have a molar ratio of 3/1. Small, more preferably smaller than 5/1. If the molar ratio is higher than this, the ratio Az / An of the Z-average molecular chain length (Az) to the number average molecular chain length (An) measured by gel permeation chromatography (GPC) is 20 to 30. And the ratio Aw / An of the weight average molecular chain length (Aw) to An, which is an index of the molecular weight distribution, is larger than 5, and the ratio of 3.8 <Log Aw <4.5 is most preferable. Ethylene-α-olefin having a monomodal or bimodal molecular weight distribution structure having a molecular chain length component having a high abundance and having a viscosity measured by an ML viscometer in the range of 60 <ML _{1 + 4} , 121 ° C. <160. It becomes difficult to satisfy the condition of non-conjugated diene copolymer rubber, and it becomes impossible to obtain a desired foam.

  The amount of carbon black is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer rubber. If the compounding amount of carbon black is larger than this, the density of the foam does not sufficiently decrease, and if it is smaller than this, there occurs a problem that the skin of the extruded product has a waving phenomenon.

  Examples of the type of carbon black used include HAF carbon, FEF carbon, high-structure FEF carbon, GPF carbon, SRF carbon, high-structure SRF carbon, and MAF carbon. These may be used alone or in combination.

  The amount of the softening agent is preferably 30 to 150 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer rubber. If the amount of the softening agent is more than this, gas escape is likely to occur and the density of the foam is not sufficiently reduced, and if the amount is less than this, the viscosity of the compound becomes too high and the density of the foam is sufficiently reduced. May not.

  As the kind of the softening material to be used, paraffin oil is preferable, and hydrogenated paraffin oil can be used.

  The amount of the foaming agent is preferably 2 to 15 parts by weight, more preferably 3 to 7 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer rubber. If the compounding amount of the foaming agent is larger than this, gas escape easily occurs and the density of the foam does not decrease sufficiently.If the compounding amount is smaller than this, the amount of gas generated from the foaming agent is insufficient and the foam is sufficiently reduced. The density may not decrease.

  Examples of the type of the blowing agent used include inorganic blowing agents such as sodium bicarbonate and ammonium bicarbonate, N, N'-dinitrosopentamethylenetetramine, azodicarbonamide, benzenesulfonylhydrazide, p, p'-oxybis (benzene Organic blowing agents such as sulfonyl hydrazide), and among them, p, p'-oxybis (benzenesulfonyl hydrazide), azodicarbonamide and a combination thereof are preferable.

  The compounding agent constituting the foam is not particularly limited, and in addition to the carbon black, the softening agent, the foaming agent, various fillers generally used for rubber compounding, processing aids, vulcanizing agents, vulcanizing agents An accelerator, a dehydrating agent and the like may be blended.

  The method for producing the copolymer rubber of the present invention is not particularly limited, and is obtained by polymerizing ethylene, α-olefin, and a non-conjugated diene in the presence of a catalyst such as a so-called Ziegler-Natta catalyst or a metallocene catalyst.

  For example, when using a Ziegler-Natta catalyst, a combination of an organoaluminum compound and a vanadium compound is preferable.As the organoaluminum compound, triethylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum dichloride, isobutyl Examples include aluminum dichloride and mixtures thereof.

  Examples of the vanadium compound include vanadium tetrahalide, vanadium oxyhalide, vanadium triacetylacetonate, vanadium oxydiliacetylacetonate, vanadium oxytrialkoxide, vanadium oxyalkoxide, and mixtures thereof. Further, in addition to the organoaluminum compound and the vanadium compound, an alcohol such as methanol or ethanol can be used in combination. In addition, hydrogen can be used as a chain transfer agent.

  Examples of using a metallocene catalyst include those obtained by polymerizing ethylene, α-olefin, and a non-conjugated diene in the presence of a catalyst using at least one transition metal complex having a cyclopentadienyl skeleton.

  As the above transition metal complex, a transition metal complex (A) represented by the following chemical formulas [I] to [III] is preferable.

The copolymer of the present invention can be optimally produced in the presence of a catalyst comprising the transition metal complex (A) and the following (B) and / or (C).
(A): transition metal complex represented by the following general formulas [I], [II], and [III]

(In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element, and J represents Group 14 of the periodic table of the element. Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, and X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, A halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a disubstituted amino group, and X ³ represents an atom belonging to Group 16 of the periodic table of the element. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily bonded to form a ring, and two M ¹ , A, J, Cp ¹ , X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.)

(B): at least one aluminum compound selected from the following (B1) to (B3) (B1) an organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) a general formula ｛-Al (E ² ) -O-} cyclic aluminoxane having the structure represented by _b (B3) formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 linear aluminoxane having a structure represented by ₂ (however, E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ may be the same or different, and Z is a hydrogen atom or a halogen atom And all Z may be the same or different. A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)

(C): a boron compound of any of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ;
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^—
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, and G ⁺ is an inorganic or organic cation. And L is a neutral Lewis base and (LH) ⁺ is a Bronsted acid.)
Hereinafter, the above-mentioned production method will be described in more detail.

  (A) The transition metal complex will be described.

In the general formulas [I], [II], and [III], the transition metal atom represented by M ¹ represents a transition metal element belonging to Group 4 of the Periodic Table of the Elements (Revised edition of IUPAC inorganic chemical nomenclature 1989), For example, a titanium atom, a zirconium atom, a hafnium atom and the like can be mentioned. Preferably it is a titanium atom or a zirconium atom.

  Examples of the atoms of Group 16 of the periodic table of the element represented by A in the general formulas [I], [II], and [III] include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable. .

  In the general formulas [I], [II], and [III], examples of atoms belonging to Group 14 of the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Is an atom.

The group having a cyclopentadiene type anion skeleton represented as the substituent Cp ^1, for example, eta ⁵ - (substituted) cyclopentadienyl group, η ⁵ - (substituted) indenyl group, η ⁵ - (substituted) fluorenyl group is there. If specifically exemplified, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetra methylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru group, eta ⁵ - neopentyl cycloalkyl Bae Ntajieniru group, eta ^{5-n-Hekishirushikurope} Ntajieniru group, eta ^5-n-octyl cyclopentane Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Na Fuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group, eta ^{5-tert-butyldimethylsilyl} cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group , eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl group, eta ⁵ - isopropylindenyl group, eta ^5-n-butyl indenyl group, eta ^5-sec- butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ^5-n-pentyl indenyl group, eta ⁵ - neopentyl indenyl group, eta ^5-n-hexyl indenyl group, eta ^5-n-octyl indenyl group, eta ^{5-n-Deshiruindeniru} group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl Indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ^{5-n-propyl-fluorenyl} group, eta ⁵ - di-n- propyl fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵ - diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group, eta ^5-tert. - butylfluorenyl group, eta ⁵ - di -n- butyl fluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ⁵ -n - pentyl fluorenyl group, eta ⁵ - Neopentyl fluorenyl group, eta ^{5-n-hexyl-fluorenyl} group, eta ^{5-n-octyl-fluorenyl} group, eta ^5-n-decyl fluorenyl group, eta ^{5-n-dodecyl-fluorenyl} group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - naphthyl fluorenyl group, η ⁵ -trimethylsilylfluorenyl group, η ⁵ -bis-trimethylsilylfluorenyl group, η ⁵ -triethylsilylfluorenyl group, η ⁵ -tert-butyldimethylsilylfluorenyl group, and the like. ⁵ - cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ^{5-tert-butylcyclopentadienyl} group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ Indenyl group, or eta ⁵ - fluorenyl group.

Examples of the halogen atom for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ^{5 and} R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Atom or bromine atom, more preferably chlorine atom.

As the alkyl group for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an alkyl group having 1 to 20 carbon atoms is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n -Dodecyl group, n-pentadecyl group, n-eicosyl group and the like, and more preferably, methyl group, ethyl group, isopropyl group, tert-butyl group or amyl group.

  Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl Perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, Bromopentadecyl group, perbromoeicosyl group and the like can be mentioned.

  All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

As the aralkyl group for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aralkyl group having 7 to 20 carbon atoms is preferable. (Methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5 -Dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) Methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethyl (Tylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) Methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl Group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decyl) Phenyl) methyl group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group Such as anthracenylmethyl group and the like, more preferably a benzyl group.

  All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

As the aryl group for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aryl group having 6 to 20 carbon atoms is preferable. For example, a phenyl group, 2-tolyl Group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5 -Xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5- Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl Group, n-propylphenyl group, isop Propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, Examples thereof include an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group and an anthracenyl group, and a phenyl group is more preferable.

  All of these aryl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituted silyl group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ^5, or R ⁶ is a silyl group substituted with a hydrocarbon group, wherein the hydrocarbon group is Is a carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, etc. Examples thereof include an alkyl group having 1 to 10 atoms and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. Di-substituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert 3 to 3 carbon atoms such as butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group and triphenylsilyl group; 20 tri-substituted silyl groups and the like, preferably trimethyl Lil group, tert- butyldimethylsilyl group, or a triphenylsilyl group.

  All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

As the alkoxy group for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an alkoxy group having 1 to 20 carbon atoms is preferable, for example, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy And a methoxy group, an ethoxy group or a tert-butoxy group.

  All of these alkoxy groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkyloxy group for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, ( 2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4- (Trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethyl Phenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2 3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) Methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octyl) Phenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group Naphthylmethoxy group, anthracenylmethoxy methoxy group and the like, more preferably a benzyloxy group.

  All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

As the aryloxy group for the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aryloxy group having 6 to 20 carbon atoms is preferable. -Methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5 -A trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group , Sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group.

  All of these aryloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The disubstituted amino group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ^5, or R ⁶ is an amino group substituted with two hydrocarbon groups. Examples of the hydrogen group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group And C6 to C10 aryl groups such as a phenyl group and C7 to C10 aralkyl groups. Examples of such a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Groups, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert-butyldimethylsilylamino group and the like, and preferably a dimethylamino group or a diethylamino group.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring.

Preferably, R ¹ is an alkyl, aralkyl, aryl or substituted silyl group.

Preferably, X ¹ and X ² are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, and more preferably a halogen atom.

Examples of the transition metal complex (A) include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclo) Pentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert -Butyl-5-chloro-2-phenoxy) titanium dichloride,
Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) tita Dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride,
Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5 -Chloro-2-phenoxy) titanium dichloride,
Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl -2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, iso Llopylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride ,
Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentane) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phen) Xy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Chloro-2-phenoxy) titanium dichloride,
Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclo) Antadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t Methylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo Antadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl 5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride , Diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) ) Titanium dichloride,
Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl -5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert- Tylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) ) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethyl Rylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenyl Methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3- tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, and titanium of these compounds is replaced with zirconium or hafnium. The compound in which dichloride was changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide, and (cyclopentadienyl) was changed to (dimethylcyclopentadiene) (Enyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), or a compound changed to (indenyl), (3,5-dimethyl-2) -Pheno B) is (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2-phenoxy), A transition metal complex wherein J in the general formula [I] is a carbon atom, such as a compound changed to (3-tert-butyldimethylsilyl-2-phenoxy) or (3-trimethylsilyl-2-phenoxy);
Dimethylsilyl (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl) -2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methyl-2 -Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2) − Enoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl- 2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5- Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopenta Enyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl ( Methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethyl Silyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titaniumdichloride Roraido,
Dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopenta Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopenta Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsi (N-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl- 2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert- Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopenta Dienyl) 3,5 diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentane) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentane) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) Titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titani Mujikuroraido, dimethylsilyl (tert- butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5 -Methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethyi) Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) Titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-) 2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titani Mujikuroraido, dimethylsilyl (trimethylsilyl cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silyl (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) Titanium dichloride,
Dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silyl (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fur Renyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-diamil -2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, and (cyclopentadienyl) of these compounds with (dimethyl Clopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), Compounds changed to (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or (phenylindenyl), (2-phenoxy) (3-phenyl 2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilyl is diethylsilyl, diphenylsilyl, or dimethoxy Compound changed to silyl, titanium In general formula [I] such as a compound in which is changed to zirconium or hafnium, and a compound in which dichloride is changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide. Is a transition metal complex which is an atom belonging to Group 14 of the periodic table of elements other than carbon atoms.

  The transition metal complex represented by the general formula [I] can be synthesized, for example, by the following method.

  That is, first, an alkoxybenzene compound having a halogenated ortho position and a cyclopentadiene compound substituted with a halogenated Group 14 atom are reacted in the presence of an organic alkali metal or magnesium metal to form a cycloalkyl compound. A compound having a structure in which a group having a pentadiene skeleton and a group having an alkoxybenzene skeleton are connected by a Group 14 atom is obtained. Then, after treating the compound with a base, the compound is reacted with a halide, a hydrocarbon, or a hydrocarbon oxy compound of a transition metal to synthesize a transition metal complex represented by the general formula [I]. it can.

  Examples of the transition metal complex represented by the general formula [II] include μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadienyl) ( 2-phenoxy) titanium methoxide, μ-oxobis {isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (Methylcyclopentadi Nil) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) tita Um chloride}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (3-tert-butyl) 5-methyl-2-phenoxy) titanium chloride ク ロ, μ-oxobis ｛dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide｝, μ-oxobis ｛dimethylsilylene (Methylcyclope (N-tadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3- tert-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ -Oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis Dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium methoxide}, and the like.

  Examples of the transition metal complex represented by the general formula [III] include di-μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene (cyclopentadiene). Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropy Lidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, Di-μ-oxobis {isopropylidene (tetramethylcyclopentadie ) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di- [mu] -oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium}, di- [mu] -oxobis} dimethylsilylene (Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ -Oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) ) Titanium｝, di-μ-oxobis ｛dimethylsilylene (tetrame Le cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, and the like.

  The transition metal complex represented by the general formula [II] or [III] can be produced by reacting the transition metal complex represented by the general formula [I] with one or two equivalents of water.

  (B) The aluminum compound will be described.

The aluminum compound (B) is one or more aluminum compounds selected from the following (B1) to (B3).
(B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane having a structure represented by the general formula ｛-Al (E ² ) -O-｝ _b (B3) General formula E ^{3 {-Al (E 3) -O-} } linear aluminoxane having a structure represented by _c AlE ³ ₂ (where, E ^1, E ^2, and E ³ are each a hydrocarbon group, all of E ¹ , all E ² and all E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different; (A number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
As the hydrocarbon group for E ¹ , E ² or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

Specific examples of the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B1), trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as tri-hexyl aluminum; dimethylaluminum chloride Dialkylaluminum chlorides, such as diethyl aluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides, such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum Yes Examples thereof include dry, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, dialkyl aluminum hydride such as dihexyl aluminum hydride, and the like.

  Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

Formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} represented by _c AlE ³ ₂ Structure Specific examples of E ² and E ^{3 in} the linear aluminoxane (B3) having the following formula: An alkyl group can be exemplified. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

  The above aluminoxanes are made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. Further, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt containing water of crystallization (for example, hydrated copper sulfate) can be exemplified.

  (C) The boron compound will be described.

As the boron compound (C), (C1) a boron compound represented by a general formula BQ ¹ Q ² Q ³ , (C2) a boron compound represented by a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (C3) any of the boron compounds represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— .

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon. Group, substituted silyl group, alkoxy group or disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substitution containing 1 to 20 carbon atoms. A silyl group, an alkoxy group having 1 to 20 carbon atoms or an amino group having 2 to 20 carbon atoms, and more preferably Q ^{1 to} Q ³ are a halogen atom and a carbon atom having 1 to 20 carbon atoms. It is a hydrogen group or a halogenated hydrocarbon group containing 1 to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q ^{1 to} Q ⁴ are each at least one fluorine atom. It is a fluorinated aryl group having 6 to 20 carbon atoms including atoms.

  Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, Tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferably, tris (pentafluorophenyl) borane is used. Phenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is a boron atom in a trivalent valence state. , Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above (C1).

Formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver cation, etc. However, examples of the organic cation G ⁺ include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

  Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylmethyltetrakis Examples thereof include (pentafluorophenyl) borate and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate. Most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

In the boron compound (C3) represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , L is a neutral Lewis base, and (LH) ⁺ a slashed.nsted acid, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

Specific examples of the Brönsted acid (LH) ^{+ in} the compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include trialkyl-substituted ammonium, N, N - dialkylanilinium, dialkylammonium and triarylphosphonium ^{mentioned, (BQ 1 Q 2 Q 3} Q 4) - as are mentioned those similar to the aforementioned.

  Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ) Ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2 , 4,6-Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate , Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) It is borate.

  In the copolymerization, an olefin polymerization catalyst using the transition metal complex (A) represented by the general formula [I] and the above (B) and / or the above (C) is used. When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) are preferred as (B). Another preferred embodiment of the olefin polymerization catalyst is an olefin polymerization catalyst using the above (A), (B) and (C). In this case, (B) is the above-mentioned (B1). ) Easy to use.

  The amount of each component used is usually a molar ratio of (B) / (A) of 0.1 to 10,000, preferably 5 to 2,000, and a molar ratio of (C) / (A) of 0.01 to 100, It is desirable to use each component so that it is preferably in the range of 0.5 to 20.

  When each component is used in a solution state or a suspension state in a solvent, the concentration is appropriately selected depending on conditions such as the performance of a device for supplying each component to the polymerization reactor. 0.01 to 500 μmol / g, more preferably 0.05 to 100 μmol / g, still more preferably 0.05 to 50 μmol / g, and (B) is usually 0.01 to 10000 μmol / g in terms of Al atom. And more preferably 0.1 to 5000 μmol / g, still more preferably 0.1 to 2000 μmol / g, and (C) is usually 0.01 to 500 μmol / g, more preferably 0.05 to 200 μmol. / G, more preferably in the range of 0.05 to 100 μmol / g.

In order to produce the copolymer of the present invention, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, benzene, aromatic hydrocarbons such as toluene, or halogenated hydrocarbons such as methylene dichloride are used. Solvent polymerization used as a solvent, slurry polymerization, gas-phase polymerization in a gaseous monomer, and the like are possible, and both continuous polymerization and batch polymerization are possible. The polymerization temperature may range from -50～250 ° C., particularly preferably in the range of -20 to 200 ° C., the polymerization pressure is atmospheric pressure to 100 kg / cm ² G are preferred. Generally, the polymerization time is appropriately determined depending on the type of the catalyst to be used and the reaction apparatus, but can range from 1 minute to 20 hours. Further, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

As a preferable polymerization method for carrying out the present invention, for example, solvent polymerization using an aliphatic hydrocarbon such as hexane, heptane, and octane as a solvent can be mentioned. The polymerization may be continuous or batchwise. The essential part of the present invention can be achieved only by carrying out the polymerization in a single-vessel polymerization, but it may be carried out by connecting two or more reactors in parallel or in series. Specifically, it is preferable to satisfy the following conditions (I) to (IV).
(I) a solution polymerization (II) a polymerization temperature of 0 to 200 ° C. (III) a residence time of 5 to 120 minutes (IV) a polymerization tank pressure of normal pressure to 100 kg / cm ² G More preferably, the low-temperature low-pressure solution method in which polymerization is carried out under the conditions of 30 ° C. to 160 ° C. and a polymerization pressure of 0 to 50 kg / cm ² G or less, in which the polymer is dissolved using a solvent such as hexane, is used. In a polymer production reactor, it can be produced efficiently.

As a specific method for obtaining the copolymer of the present invention, for example, the following method using two or more reaction vessels is exemplified.
(1) A monomodal copolymer having a peak at 3.8 <Log Aw <4.5 in GPC measurement in the first polymerization reaction tank and having an Aw / An ratio of 2 to 4 is obtained. Log Aw and Aw / An ratio are controlled by the amount of hydrogen and the polymerization temperature, respectively.
(2) In the presence of the copolymer obtained in the first polymerization reaction tank, in a tank subsequent to the second polymerization reaction tank, a monomodal having a peak at 2.5 <Log Aw <3.5, and And a copolymer having an Aw / An ratio of 2 to 4 is obtained. Log Aw and Aw / An ratio are controlled by the amount of hydrogen and the polymerization temperature, respectively.

  The preferable polymerization temperature at this time is in the range of 40 to 65 ° C., and the copolymer content in the polymerization solution is 3 to 15% by weight.

  Although the method for obtaining the copolymer of the present invention by connecting the polymerization tanks in series has been described, two or more polymerization reaction tanks are arranged in parallel, and the above-mentioned (1) and (2) are used in each polymerization reaction tank. It can also be obtained by obtaining copolymers satisfying the conditions shown and mixing them.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[I] Preparation method of copolymer rubber
Copolymer rubber 1 ( Copolymer rubber satisfying the conditions of the present invention)
Ethylene, propylene, and 5-ethylidene-2-norbornene were continuously copolymerized using two 100 L SUS polymerization vessels equipped with stirring blades in series. That is, from the lower part of the first polymerization vessel, hexane was used as a polymerization solvent at a rate of 118 kg / hour, and ethylene, propylene and 5-ethylidene-2-norbornene were used as monomers at 3.54 kg / hour, 12.03 kg / hour, and 0.13 kg / hour. At a rate of 58 kg / hour, vanadium oxytrichloride and ethylaluminum sesquichloride were continuously supplied as catalysts from the lower part of the reactor to the reactor at a rate of 0.0063 kg / hour and 0.032 kg / hour, respectively. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization vessel became 100 L. The molecular weight was adjusted with hydrogen. The polymerization solution withdrawn from the first polymerization reactor is supplied from the lower part of the second polymerization reactor, and hexane is used as a polymerization solvent at a rate of 79 kg / hour from the lower part of the second polymerization reactor. Polymerization of ethylidene-2-norbornene at a rate of 1.0 kg / hour and 0.436 kg / hour, respectively, and vanadium oxytrichloride and ethyl aluminum sesquichloride as catalysts at a rate of 0.029 kg / hour and 0.086 kg / hour, respectively. It was continuously fed into the vessel. The molecular weight was adjusted with hydrogen. In the copolymerization reaction, the first polymerization reactor was controlled at 47 ° C. and the second polymerization reactor was controlled at 60 ° C. by supplying low-pressure steam to a jacket provided outside the polymerization reactor. A small amount of ethanol was added to the polymerization solution withdrawn from the polymerization vessel to stop the polymerization reaction, and after removing the monomer and washing with water, the solvent was removed by steam in a large amount of water to take out the copolymer, and the pressure was reduced at 80 ° C day and night. Dried. By the above operation, ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber was produced at a rate of 6.5 kg / hour.

Copolymer rubber 2 ( Copolymer rubber satisfying the conditions of the present invention)
The supply amounts of 5-ethylidene-2-norbornene to the first and second polymerization reactors were 0.606 kg / hour and 0.422 kg / hour, respectively, and vanadium oxytrichloride to the first and second polymerization reactors was used. And the supply amount of ethyl aluminum sesquichloride was 0.026 kg / hour and 0.071 kg / hour, respectively. Was the same as copolymer rubber 1 except that the polymerization reactor was controlled at 57 ° C. A copolymer rubber was obtained at a rate of 6.5 kg / hour.

Copolymer rubber 3 ( Copolymer rubber satisfying the conditions of the present invention)
Copolymerization of ethylene, propylene, 5-ethylidene-2-norbornene, and dicyclopentadiene was continuously performed using two 100 L SUS polymerization vessels equipped with stirring blades in series. That is, from the lower part of the first polymerization vessel, hexane was used as a polymerization solvent at a rate of 118 kg / hour, and ethylene, propylene, 5-ethylidene-2-norbornene, and dicyclopentadiene were used as monomers at 3.52 kg / hour and 11.96 kg / hour, respectively. Vanadium oxytrichloride and ethylaluminum sesquichloride were used as catalysts at a rate of 0.80 kg / hr and 0.09 kg / hr, respectively, at a rate of 0.0067 kg / hr and 0.033 kg / hr, respectively, from the lower part of the reactor. Feeded continuously during. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization vessel became 100 L. The molecular weight was adjusted with hydrogen. The polymerization solution withdrawn from the first polymerization reactor is supplied from the lower part of the second polymerization reactor, and hexane is used as a polymerization solvent at a rate of 79 kg / hour from the lower part of the second polymerization reactor. Ethylidene-2-norbornene and dicyclopentadiene were added at a rate of 1.0 kg / hr, 0.39 kg / hr and 0.04 kg / hr, respectively, and vanadium oxytrichloride and ethylaluminum sesquichloride were added as catalysts at a rate of 0.024 kg / hr. , At a rate of 0.072 kg / hr. The molecular weight was adjusted with hydrogen. In the copolymerization reaction, the first polymerization reactor was controlled at 47 ° C. and the second polymerization reactor was controlled at 57 ° C. by supplying low-pressure steam to a jacket provided outside the polymerization reactor. A small amount of ethanol was added to the polymerization solution withdrawn from the polymerization vessel to stop the polymerization reaction, and after removing the monomer and washing with water, the solvent was removed by steam in a large amount of water to take out the copolymer, and the pressure was reduced at 80 ° C day and night. Dried. By the above operation, ethylene-propylene-5-ethylidene-2-norbornene-dicyclopentadiene copolymer rubber was produced at a rate of 6.4 kg / hour.

Copolymer rubber 4 ( Copolymer rubber satisfying the conditions of the present invention)
The supply amounts of 5-ethylidene-2-norbornene to the first polymerization reactor and the second polymerization reactor were 0.51 kg / hour and 0.34 kg / hour, respectively, and the supply amounts of dicyclopentadiene were 0.10 kg / hour and 0, respectively. 0.05 kg / hour, the supply amounts of vanadium oxytrichloride to the first polymerization reactor and the second polymerization reactor were 0.0071 kg / hour and 0.026 kg / hour, respectively, and the supply amount of ethyl aluminum sesquichloride was 0.036 kg / hour. The time was 0.079 kg / hour, and the same as the copolymer rubber 1 except that the first polymerization reactor was controlled at 47 ° C. and the second polymerization reactor was controlled at 60 ° C. A copolymer rubber was obtained at a rate of 6.6 kg / hour.

Copolymer rubber 5 ( Copolymer rubber that does not satisfy the conditions of the present invention)
Ethylene, propylene, and 5-ethylidene-2-norbornene were continuously copolymerized using two 100 L SUS polymerization vessels equipped with stirring blades in series. That is, from the lower part of the first polymerization vessel, hexane as a polymerization solvent was used at a rate of 108 kg / hour, and ethylene, propylene, and 5-ethylidene-2-norbornene were used as monomers at 2.37 kg / hour, 13.00 kg / hour, and 0. Vanadium oxytrichloride and ethylaluminum sesquichloride were continuously supplied as catalysts from the lower part of the polymerization vessel into the polymerization vessel at a rate of 40 kg / hr at a rate of 0.0035 kg / hr and 0.028 kg / hr, respectively. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization vessel became 100 L. The polymerization solution withdrawn from the first polymerization reactor is supplied from the lower part of the second polymerization reactor, and hexane is used as a polymerization solvent at a rate of 98 kg / hour from the lower part of the second polymerization reactor. Polymerization of ethylidene-2-norbornene at a rate of 0.9 kg / hour and 0.358 kg / hour, respectively, and vanadium oxytrichloride and ethylaluminum sesquichloride as catalysts at a rate of 0.011 kg / hour and 0.057 kg / hour, respectively. It was continuously fed into the vessel. The molecular weight was adjusted with hydrogen. In the copolymerization reaction, low pressure steam was supplied to a jacket attached to the outside of the polymerization vessel, whereby the first polymerization vessel was controlled at 50 ° C and the second polymerization vessel was controlled at 55 ° C. A small amount of ethanol was added to the polymerization solution withdrawn from the polymerization vessel to stop the polymerization reaction, and after removing the monomer and washing with water, the solvent was removed by steam in a large amount of water to take out the copolymer, and the pressure was reduced at 80 ° C day and night. Dried. By the above operation, ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber was produced at a rate of 4.3 kg / hour.

Copolymer rubber 6 ( Copolymer rubber that does not satisfy the conditions of the present invention)
The feed rates of hexane, ethylene, propylene, and 5-ethylidene-2-norbornene in the first polymerization vessel were increased at a rate of 13.0 kg / hour, 3.56 kg / hour, 17.0 kg / hour, and 0.52 kg / hour, respectively. Vanadium oxytrichloride and ethylaluminum sesquichloride were used as catalysts at a rate of 0.0050 kg / hour and 0.040 kg / hour, respectively, and the supply amount of hexane, ethylene and 5-ethylidene-2-norbornene in the second polymerization reactor was 98 kg each. / Hour, 1.29 kg / hour, and 0.46 kg / hour at a rate of 0.016 kg / hour and 0.081 kg / hour of vanadium oxytrichloride and ethylaluminum sesquichloride as catalysts, respectively. The first was controlled at 53 ° C and the second at 58 ° C. Except for the above, the procedure was the same as that for the copolymer 5, and the ethylene-propylene-5-ethylidene-2-norbornene copolymer was used at a rate of 5.9 kg / hour.

Copolymer rubber 7 ( Copolymer rubber that does not satisfy the conditions of the present invention)
Esplen E-5216 manufactured by Sumitomo Chemical Co., Ltd. was used as it was.

Copolymer rubber 8 ( Copolymer rubber that does not satisfy the conditions of the present invention)
Esplen E-5206F manufactured by Sumitomo Chemical Co., Ltd. was used as it was.

Copolymer rubber 9 ( Copolymer rubber that does not satisfy the conditions of the present invention)
Esplen E-5503 manufactured by Sumitomo Chemical Co., Ltd. was used as it was.

Copolymer rubber 10 ( Copolymer rubber that does not satisfy the conditions of the present invention)
Exxon Vistalon V-8600 was used as it was.

[II] Method of measuring copolymer The properties of the polymer were measured by the following method.

(1) Propylene content Using an infrared spectrophotometer (IR-810, manufactured by JASCO Corporation), an infrared absorption spectrum (IR spectrum) of polypropylene, polyethylene, ethylene-propylene copolymer (50:50) was obtained. It measured using as a standard product. The measurement sample was measured as a film of about 0.1 mm using a hot press machine. The measured values are in accordance with literature values (characterization of polyethylene by infrared absorption spectrum, written by Takayama, Usami et al. Or Die Makromolekulare Chemie, 177, 461 (1976) Mc Rae, MA, MadamS, WF, etc.). Using the absorption peak at 1155 cm ^-1 (methyl branch) as a marker, the average value was determined as the value measured three times.

(2) Iodine value The copolymer was hot pressed to form a 0.5 mm thick film, and then a peak (wave number) derived from dicyclopentadiene and 5-ethylidene-2-norbornene was measured using an infrared spectrometer. 1611 cm ^-1 , 1688 cm ^-1 ) The transmittance was determined, and the molar content of double bonds in the copolymer was calculated and converted to iodine value.

(3) Molecular weight and molecular weight distribution The measurement is performed using a gel permeation chromatograph (150C / GPC apparatus manufactured by Waters). The elution temperature is 140 ° C., the column used is Showa Denko Corporation, Shodex Packed Column A-80M, the molecular weight standard substance is polystyrene (for example, Tosoh Corporation, molecular weight 68-8,400,000), and the weight average molecular weight in terms of polystyrene is used. The chain length (Aw), number average molecular chain length (An), and Z-average molecular chain length (Az) were obtained. The measurement sample is prepared by dissolving about 5 mg of the polymer in 5 ml of o-dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected, and the elution solvent flow rate was set to 1.0 ml / min, and detected by a refractive index detector.

(4) Stress Relaxation Rate The stress relaxation behavior at 80 ° C. was measured using a fully automatic stress relaxation measurement device (made by Island Industry Co., Ltd.). A rubber sample press-molded to a thickness of 4 mm was punched out with a punch having a diameter of 7 mm to obtain a measurement sample. The measurement was performed in a compression mode, the amount of strain was 20%, the reference time was 0.01 seconds, the sample temperature was 80 ° C., and the stress after 0.01 seconds and 100 seconds after applying the strain were measured.

[III] Evaluation method of kneading processability Using a BR-600 mixer (0.6 L) manufactured by Toyo Seiki Co., Ltd., knead the copolymer rubber prepared by the above method with various compounding agents shown in Tables 3 and 4, and The time until the peak of the dispersion process appeared (BIT: Black Incorporation Time) was examined. The ram pressure was 2 kg / cm ² ), the rotor speed was 50 rpm, the circulating oil temperature was 80 ° C., and the rubber mastication time was 30 seconds. Specific examples of the BIT are, for example, “Rubber Test Method <New Edition>”, 2nd edition, Japan Rubber Association p. 176. Is shown in

[IV] Method of evaluating foam properties (1) Preparation of composition 100 parts by weight of copolymer rubber 1 shown in Table 5, 110 parts by weight of GPF carbon (Asahi 55G manufactured by Asahi Carbon Co., Ltd.), paraffin oil (manufactured by Idemitsu Kosan Co., Ltd.) Diana PS-430) 63 parts by weight, heavy calcium carbonate (NS-200 manufactured by Nitto Powder Chemical Co., Ltd.) 20 parts by weight, composite zinc oxide (Meta Z102 manufactured by Inoue Lime Co., Ltd.) 5 parts by weight, stearic acid 1 part by weight, average 1 part by weight of polyethylene glycol having a molecular weight of 4000, 2 parts by weight of a processing aid (1) (Stractol WB42 manufactured by S & S), and 2 parts by weight of a processing aid (2) (Actiplast by Bayer) having a content volume of 1.7 L The mixture was kneaded at 60 rpm for 5 minutes using a Banbury type mixer (BB-2 mixer manufactured by Kobe Steel). After cooling the obtained composition to room temperature, it was wound around a 10-inch open roll whose temperature was controlled to 40 ° C., and 5 parts by weight of calcium oxide (Vesta PP manufactured by Inoue Lime Co., Ltd.) per 100 parts by weight of the copolymer was cured. 1.5 parts by weight of sulfur as an agent, 0.63 parts by weight of ethylenethiourea masterbatch (ETU-80 manufactured by Lane Chemie) and 0.53 part of dibenzothiazyl disulfide masterbatch (MBTS-75 manufactured by Lane Chemie) as a vulcanization accelerator Parts by weight, 1.0 part by weight of 2-mercaptobenzothiazole masterbatch (MBT-80 manufactured by Lane Chemie), 0.63 parts by weight of dipentamethylenethiuram tetrasulfide masterbatch (DPTT-70 manufactured by Lane Chemie), zinc-amine- Dithiophosphate complex (ZAT-70 manufactured by Lane Chemie) 1 2 parts by weight, p, p'-oxybis (benzene sulfonyl hydrazide) were mixed (Sankyo Kasei Neoserubon # 1000) 3.5 parts by weight.

The blended compositions using the copolymer rubbers 2 to 7 were similarly adjusted except that the copolymer used was different.
(2) Vulcanization and foaming The prepared composition was extruded into a cylindrical shape using a 45 mmφ extruder (L / D = 16), and was continuously introduced into a hot air vulcanization tank whose temperature was adjusted to 230 ° C. did. The residence time in the hot air vulcanization tank was 5 minutes.
(3) Density The density of the foam obtained by vulcanization foaming was determined by an underwater substitution method.
(4) Tensile Properties A test piece was punched out from a foam obtained by vulcanization and foaming using a JIS No. 3 dumbbell and subjected to a tensile test. The tensile speed was 500 mm / min.
(5) Compression Permanent The foam obtained by vulcanization and foaming was kept at 70 ° C. for 22 hours while being compressed to a height of 50%. It was opened after a predetermined time, the height after 30 minutes was measured, and the compression set value was determined.

  Compression set (%) = 50 × [(original sample height) − (sample height after compression heat treatment)] / (original sample height)

＊１ ＥＮＢ：５−エチリデン−２−ノルボルネン
＊２ ＤＣＰＤ：ジシクロペンタジエン
＊３ 100×（100秒後の応力）／（０．０１秒後の応力）

* 1 ENB: 5-ethylidene-2-norbornene * 2 DCPD: dicyclopentadiene * 3 100 × (stress after 100 seconds) / (stress after 0.01 seconds)

Claims (5)

The ratio Az / An between the Z-average molecular chain length (Az) and the number average molecular chain length (An) measured by gel permeation chromatography (GPC) is in the range of 20 to 30, and is an index of the molecular weight distribution. The ratio Aw / An of the weight average molecular chain length (Aw) to An is greater than 5, and a monomodal or bimodal molecular weight distribution structure having a peak in the range of 3.8 <Log Aw <4.5. A foam obtained by using an ethylene-α-olefin-non-conjugated diene copolymer rubber having a viscosity measured by an ML viscometer in the range of 60 <ML _{1 + 4} and 121 ° C. <160. 2. The ethylene copolymer according to claim 1, wherein the weight ratio of the ethylene unit to the α-olefin unit in the copolymer rubber is in the range of 80/20 to 45/55, and the non-conjugated diene content is in the range of 5 to 35 in terms of iodine value. A foam obtained using an α-olefin-non-conjugated diene copolymer rubber. The non-conjugated diene is 5-ethylidene-2-norbornene alone or in combination with 5-ethylidene-2-norbornene and dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl norbornene, or 5-ethylidene-2-norbornene and norbornadiene. A foam obtained by using the ethylene-α-olefin-non-conjugated diene copolymer rubber according to claim 1 or 2. The ratio of the Z-average molecular weight (Az) and the residual compressive stress ratio after 100 seconds to the stress after 0.01 seconds after compression at 80 ° C. and 50% compression, wherein Az / residual compressive stress ratio is 2700 or less. A foam obtained by using the ethylene-α-olefin-nonconjugated diene copolymer rubber according to claim 2. Carbon black 50 to 200 parts by weight, softener 30 to 150 parts by weight, foaming based on 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer rubber according to any one of claims 1 to 4. A foam obtained by vulcanizing and foaming a rubber composition containing 2 to 15 parts by weight of an agent.