JP2009227995A - Diene polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a diene polymer and a method for producing the same. <P>SOLUTION: This polymer includes a specific recurring unit having a 6-membered ring and also a specific recurring unit having a 5-membered ring, and also a ≥70 mol% in the amount of the specific recurring unit having the 6-membered ring to the total amount of the specific recurring unit having the 6-membered ring and the specific recurring unit having the 5-membered ring. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a diene polymer and a method for producing the same.

  As the diene polymer, for example, Non-Patent Documents 1 and 2 describe a diene polymer obtained by cyclopolymerizing 1,6-heptadiene or the like.

Phillip D. Hustad, Jun Tian, and Geoffrey W. Coates, Mechanism of Propylene Insertion Using Bis (phenoxyimine) -Based Titanium Catalysts: An Unusual Secondary Insertion of Propylene in a Group IV Catalyst System, J. AM. CHEM. SOC. 2002 , 124, 3614-3621 Daisuke Takeuchi, Ryuichi Matsuura, Sehoon Park, and Kohtaro Osakada, Cyclopolymerization of 1,6-Heptadienes Catalyzed by Iron and Cobalt Complexes: Synthesis of Polymers with Trans- or Cis-Fused 1,2-Cyclopentanediyl Groups Depending on the Catalyst, J. AM. CHEM. SOC. 2007, 129, 7002-7003

  Diene polymers are expected to be used in various fields as automobile materials, home appliance parts, etc., and development of new diene polymers is strongly demanded.

  An object of the present invention is made in view of such circumstances, and is to provide a new diene polymer and a production method thereof.

<1. Polymer according to the present invention>
The polymer according to the present invention has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), the repeating unit represented by the following formula (1) and the following formula ( The amount of the repeating unit represented by the following formula (1) with respect to the total amount of the repeating unit represented by 2) is 70 mol% or more.

(In the above formula (1), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (2), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)
Moreover, the manufacturing method of the polymer which concerns on this invention makes the diene compound represented by following formula (5) into at least 1 type among the nickel compound represented by following formula (6), an organoaluminum compound, and a boron compound. Is polymerized in the presence of a catalyst formed by contacting them.

(In the above formula (5), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (6), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other, R ^{5 to} R ⁸ each independently represents a hydrocarbon group having 3 to 30 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, or a siloxy group. A group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, an amide group, an imide group, or a hydrocarbon thio group)

  According to the present invention, a new diene polymer can be provided.

  The polymer according to the present invention has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (1). The amount of the repeating unit represented by the following formula (1) with respect to the total amount of the unit and the repeating unit represented by the following formula (2) is 70 mol% or more.

(In the above formula (1), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (2), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)
Thus, the polymer according to the present invention includes a 5-membered ring structure and a 6-membered ring structure, and improves the molar ratio of the 6-membered ring structure. This is a polymer not obtained from Non-Patent Documents 1 and 2.

A ^{1 to} A ⁸ in the formulas (1) and (2) may be each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

The hydrocarbon group having 1 to 6 carbon atoms of A ^{1 to} A ^{8 in} the formulas (1) and (2) may have 1 to 6 carbon atoms. Examples of the hydrocarbon group include a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group.

  Examples of the linear hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  Examples of the branched hydrocarbon group include an isopropyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group.

  Examples of the cyclic hydrocarbon group include a phenyl group and a cyclohexyl group.

  Specific examples of the repeating units represented by the above formulas (1) and (2) include the following formulas (3) and (4), respectively.

The repeating unit represented by these can be mentioned.

  In the present invention, the amount of the repeating unit represented by the above formula (1) relative to the total amount of the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) (hereinafter described) For the sake of convenience, the “content of 6-membered ring” may be 70 mol% or more. The upper limit is not limited as long as it is a copolymer of the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2), and it can also be said to be less than 100 mol%.

  In addition, 6-membered ring content can be measured with a well-known measuring method, for example, is good to measure using NMR. Moreover, you may measure by the method of Example 1 mentioned later.

  The weight average molecular weight (Mw) of the polymer according to the present invention is preferably 1,000 to 10,000,000, more preferably 2,000 to 5,000,000, and most preferably 4,000. ~ 3,000,000.

  The molecular weight distribution of the polymer according to the present invention is preferably 1 to 100, more preferably 1 to 50, and most preferably 1 to 20.

  The glass transition point (a measure of heat resistance) of the polymer according to the present invention is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and most preferably 300 ° C. or higher.

<2. Manufacturing method according to the present invention>
In the method for producing a polymer according to the present invention, a diene compound represented by the following formula (5) is contacted with a nickel compound represented by the following formula (6) and at least one of an organoaluminum compound and a boron compound. The polymer may be produced by polymerizing in the presence of the catalyst formed.

(In the above formula (5), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (6), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other; ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, an aralkyloxy group, or an aryloxy group, and R ^{5 to} R ⁸ represent Each independently represents a hydrocarbon group having 3 to 30 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, Represents an aralkyloxy group, an aryloxy group, an amino group, an amide group, an imide group, or a hydrocarbon thio group)
[2-1. Monomer]
The diene compound represented by the formula (5) may be a known compound, and preferably one of A ^{1 to} A ⁷ is one of A ² and A ³ and one of A ⁶ and A ⁷ is a methyl group. compound all the others are hydrogen atoms ^there, among ^{a 2, a 3, a 6} , a 7 are all others are hydrogen atom a methyl group compound of a 1 to a ^7, the a 1 to a ⁷ of a ⁴ and a ⁵ is a methyl group and compounds in which all the others are hydrogen atoms, compounds wherein a ¹ other a hydrogen atom are all methyl groups of a ¹ to a ^7, or 1,6 Heptadiene, more preferably 1,6-heptadiene. The diene compound may be used in combination of two or more.

[2-2. catalyst〕
The catalyst used for the polymerization of the diene compound may be any catalyst formed by contacting the nickel compound represented by the above formula (6) with at least one of the organoaluminum compound and the boron compound.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² in Formula (6) include an alkyl group and an aryl group. These groups may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, and an n-butyl group. Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and neopentyl group. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclooctyl group. Among them, preferred is an alkyl group having 1 to 20 carbon atoms, more preferred is a linear alkyl group having 1 to 12 carbon atoms, and further preferred is a methyl group or an ethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a 4-tolyl group, and a mesityl group. Among them, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group or a mesityl group is more preferable.

When R ¹ and R ² in Formula (6) are bonded to each other, examples of the ring formed by the bond include an aliphatic ring and an aromatic ring. These rings may have a substituent. Examples of the divalent group formed by the bond between R ¹ and R ² in the aliphatic ring include 1,2-ethylene group, 1,2-cyclohexylene group, 1,2-norbornene group, 2,3- Examples include butene, 2,3-dimethyl-2,3-butene, and 2,4-pentene. Examples of the divalent group formed by the bond between R ¹ and R ² in the aromatic ring include a 1,2-phenylene group and an acenaphthyl group, and an acenaphthyl group is preferable.

R ^{5 to} R ⁸ in Formula (6) may be any hydrocarbon group having 3 to 30 carbon atoms, and may be a linear hydrocarbon group, a branched hydrocarbon group, or a hydrocarbon group having a cyclic structure. Etc.

  Examples of the linear hydrocarbon group include an alkyl group having 3 to 30 carbon atoms such as a propyl group, a butyl group, a pentyl group, and a hexyl group. Of these, a propyl group and a butyl group are preferable.

  Examples of the branched hydrocarbon group include an alkyl group having 3 to 30 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, and ter-butyl group. Of these, isopropyl group and isobutyl group are preferable.

  The cyclic structure may be a monocyclic structure or a polycyclic structure. Further, for example, it may be an aromatic cyclic group obtained by removing one or more hydrogen atoms from an aromatic compound such as benzene or naphthalene, or may be a hydrocarbon group having an aliphatic cyclic structure. . A functional group such as an alkyl group may be further bonded to these cyclic structures. Of these, a cyclohexyl group, a phenyl group and the like are preferable.

Examples of the halogen atom of R ⁹ and R ¹⁰ in formula (6) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a chlorine atom or a bromine atom is preferable.

Examples of the alkyl group represented by R ⁹ and R ¹⁰ in Formula (6) include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, and an n-butyl group. Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group and neopentyl group. Examples of the cyclic alkyl group include cyclohexyl and cyclooctyl. The alkyl group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, preferred is an alkyl group having 1 to 20 carbon atoms, more preferred is a linear unsubstituted alkyl group having 1 to 12 carbon atoms, and further preferred is a methyl group.

Examples of the aralkyl group of R ⁹ and R ¹⁰ in formula (6) include a benzyl group and a phenethyl group. The aralkyl group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, preferably an aralkyl group having 7 to 12 carbon atoms, more preferably an unsubstituted aralkyl group having 7 to 12 carbon atoms, and further preferably a benzyl group.

Examples of the aryl group of R ⁹ and R ¹⁰ in formula (6) include a phenyl group, a naphthyl group, a 4-tolyl group, a mesityl group, and a 4-phenylphenyl group. The aryl group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group, a 4-tolyl group, or a mesityl group is more preferable.

The silyl group of R ⁹ and R ¹⁰ in Formula (6) may have a substituent. Examples of the substituted silyl group include a monosubstituted silyl group, a disubstituted silyl group, and a trisubstituted silyl group. Examples of the monosubstituted silyl group include a methylsilyl group, an ethylsilyl group, and a phenylsilyl group. Examples of the disubstituted silyl group include a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group. Examples of the trisubstituted silyl group include trimethylsilyl group, trimethoxysilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, triethylsilyl group, triethoxysilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri- n-butylsilyl group, tri-sec-butylsilyl group, tert-butyldimethylsilyl group, triisobutylsilyl group, tert-butyldiphenylsilyl group, n-hexyldimethylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, etc. It can be illustrated. The substituted silyl group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, preferably a trialkylsilyl group, more preferably a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, an n-hexyldimethylsilyl group, or a triisopropylsilyl group. It is.

The siloxy groups of R ⁹ and R ¹⁰ in Formula (6) may have a substituent. Examples of substituted siloxy groups include trimethylsiloxy group, trimethoxysiloxy group, dimethylmethoxysiloxy group, methyldimethoxysiloxy group, triethylsiloxy group, triethoxysiloxy group, tri-n-propylsiloxy group, triisopropylsiloxy group, tri-isopropylsiloxy group n-butylsiloxy group, tri-sec-butylsiloxy group, tert-butyldimethylsiloxy group, triisobutylsiloxy group, tert-butyldiphenylsiloxy group, n-hexyldimethylsiloxy group, tricyclohexylsiloxy group, and triphenylsiloxy group Etc. can be illustrated. The substituted siloxy group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, preferably a trialkylsiloxy group, more preferably a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, an n-hexyldimethylsiloxy group, or a triisopropylsiloxy group It is a group.

As the alkoxy group of R ⁹ and R ¹⁰ in the formula (6), a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group , Neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, and n-eicosyloxy group. The alkoxy group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, preferred is an alkoxy group having 1 to 20 carbon atoms, more preferred is a methoxy group, an ethoxy group, an isopropoxy group or a tert-butoxy group.

As the aralkyloxy group for R ⁹ and R ¹⁰ in the formula (6), a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (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-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5- (Limethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethyl) Phenyl) 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-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, and anthracenylmethoxy group Can be illustrated. The aralkyloxy group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among them, an aralkyloxy group having 7 to 20 carbon atoms is preferable, and a benzyloxy group is more preferable.

As the aryloxy groups of R ⁹ and R ¹⁰ in formula (6), phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethyl Phenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert -Butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethyl Phenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6- Limethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6 -Di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethyl Phenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl -3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenol Noxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy 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, naphthoxy group, and anthracenoxy group it can. The aryloxy group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group. Among these, an aryloxy group having 6 to 20 carbon atoms is preferable.

The amino groups of R ⁹ and R ¹⁰ in Formula (6) may have a substituent. Examples of the substituted amino group include a linear alkylamino group, a branched alkylamino group, and a cyclic alkylamino group. Examples of the linear alkylamino group include N-methylamino group, N-ethylamino group, N, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, and N, Examples thereof include N-di-n-butylamino group. Examples of the branched alkylamino group include N, N-diisopropylamino group, N, N-diisobutylamino group, N, N-di-tert-butylamino group, and N, N-dineopentylamino group. it can. Examples of the cyclic alkylamino group include an N, N-dicyclohexylamino group and an N, N-dicyclooctylamino group. The substituted amino group may further have a substituent. Examples of the substituent include halogen atoms, alkyloxy groups, aryloxy groups, aralkyloxy groups, nitro groups, amino groups, amide groups, imide groups, silyl groups, siloxy groups, sulfonyl groups, and hydrocarbon thio groups. it can.

The amide group of R ⁹ and R ¹⁰ in Formula (6) may have a substituent. As the substituted amide group, an ethaneamide group, an Nn-butylethaneamide group, an N-methylethaneamide group, an N-ethylethaneamide group, an Nn-butylhexaneamide group, an isopropanamide group, and an isobutanamide group , Tert-butanamide group, neopentanamide group, cyclohexaneamide group and cyclooctaneamide group. The substituted amide group may further have a substituent. Examples of the substituent include halogen atoms, alkyloxy groups, aryloxy groups, aralkyloxy groups, nitro groups, amino groups, amide groups, imide groups, silyl groups, siloxy groups, sulfonyl groups, and hydrocarbon thio groups. it can.

The imide group of R ⁹ and R ¹⁰ in Formula (6) may have a substituent. Examples of the substituted imide group include a succinimide group, a maleimide group, and a phthalimide group. The substituted imide group may further have a substituent. Examples of the substituent include halogen atoms, alkyloxy groups, aryloxy groups, aralkyloxy groups, nitro groups, amino groups, amide groups, imide groups, silyl groups, siloxy groups, sulfonyl groups, and hydrocarbon thio groups. it can.

Examples of the hydrocarbon thio group of R ⁹ and R ¹⁰ in Formula (6) include an alkylthio group, an arylthio group, and an aralkylthio group. Examples of the alkylthio group include a methylthio group, an ethylthio group, an isopropylthio group, and a tert-butylthio group. Examples of the arylthio group include a phenylthio group and a naphthylthio group. Examples of the aralkylthio group include a benzylthio group and a 9-fluorenylmethylthio group. The hydrocarbon thio group may further have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, and a silyl group.

R ⁹ and R ¹⁰ in Formula (6) are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, still more preferably a methyl group, an ethyl group, an n-propyl group, An isopropyl group, an n-butyl group, or an isobutyl group.

  Examples of the nickel compound represented by the formula (6) include dibromo [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)]. And nickel, dibromo [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-dicyclohexylaniline-κN)] nickel, and the like.

In the polymerization of the diene compound, the organoaluminum compound for generating the catalyst may be a known organoaluminum compound. As the organoaluminum compound, compounds represented by the following formulas (I) to (III) can be exemplified. The compound illustrated here may be used independently and may use 2 or more types together.
E ¹ _d AlX ² _3-d (I)
An organoaluminum compound represented by:
_{^{{-Al (E 2) -O-}}} e (II)
And a cyclic aluminoxane represented by: E ³ {—Al (E ³ ) —O—} _f AlE ³ ₂ (III)
A linear aluminoxane represented by:
In the above formulas (I) to (III), E ¹ , E ² and E ³ each independently represent a hydrocarbon group, and when there are a plurality of E ¹ , a plurality of E ² or a plurality of E ³ , May be the same or different. X ² represents a hydrogen atom or a halogen atom, and when there are a plurality of X ² , they may be the same or different. d represents a number satisfying 0 <d ≦ 3, e is an integer of 2 or more, preferably an integer of 2 to 40, and f is an integer of 1 or more, preferably an integer of 1 to 40 .

The hydrocarbon group for E ¹ , E ² and E ³ is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, and neopentyl group. Of these, a methyl group or an isobutyl group is preferable.

  Examples of the organoaluminum compound represented by the above formula (I) include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum. Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride. Examples of the alkylaluminum dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Among them, preferred is trialkylaluminum, and more preferred is triethylaluminum or triisobutylaluminum.

  The cyclic and linear aluminoxanes represented by the above formulas (II) and (III) can be produced by various methods. These manufacturing methods may be known manufacturing methods. As a production method, a method in which a trialkylaluminum such as trimethylaluminum is dissolved in an organic solvent such as benzene and an aliphatic hydrocarbon is brought into contact with water, and a trialkylaluminum such as trimethylaluminum is added to an aqueous solution of copper sulfate. An example is a method of producing by contacting with a metal salt containing water of crystallization such as a Japanese product.

In the polymerization of the diene compound, the boron compound for generating the catalyst may be a known boron compound. Examples of the boron compound include compounds represented by the following formulas (IV) to (VI):
BQ ¹ Q ² Q ³ (IV)
A boron compound represented by:
G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (V)
And (J-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (VI)
Boron compound represented by

However, in the above formula (IV) ~ (VI), B represents a boron atom in the trivalent valence ^state, and Q 1 to Q ⁴ are each independently a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, Represents a silyl group, a siloxy group, an alkoxy group or an amino group, an amide group, an imide group, G ⁺ represents an inorganic or organic cation, J represents a neutral Lewis base, and (JH) ⁺ represents a Bronsted acid. Represents.

Q ^{1 to} Q ⁴ in the above formulas (IV) to (VI) are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms. A silyl group having 1 to 20 carbon atoms, a siloxy group having 1 to 20 carbon atoms, an amino group substituted with a hydrocarbon group having 2 to 20 carbon atoms, an amide group substituted with a hydrocarbon group having 2 to 20 carbon atoms , An imide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms or a carbon atom having 1 to 20 carbon atoms. A halogenated hydrocarbon group containing an atom, more preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, particularly preferably containing at least one fluorine atom. Carbon atom 6-20 fluorinated aryl group.

  As the boron compound represented by the above formula (IV), 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, and phenylbis (pentafluorophenyl) borane. Of these, tris (pentafluorophenyl) borane is most preferable.

Examples of G ⁺ that is an inorganic cation in the boron compound represented by the above formula (V) include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. A triphenylmethyl cation can be illustrated as G ⁺ which is an organic cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation.

As (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ in the above formula (V), tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4) , 5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, and tetrakis An example is (3,5-bistrifluoromethylphenyl) borate.

  As the boron compound represented by the above formula (V), lithium tetrakis (3,5-bistrifluoromethylphenyl) borate, sodium tetrakis (3,5-bistrifluoromethylphenyl) borate, potassium tetrakis (3,5-bistrifluoro) Methylphenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrabutylphosphonium tetrakis (pentafluorophenyl) ) Borate, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethylsulfate Illustrative examples include nium tetrakis (pentafluorophenyl) borate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate can do. Of these, triphenylcarbenium tetrakis (pentafluorophenyl) borate is most preferable.

Examples of (J—H) ⁺ in the above formula (VI) include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium and triarylphosphonium, and (BQ ¹ Q ² Q ³ Q ⁴ ) ^- specific examples of can be exemplified the same as those exemplified in the explanation of the above formula (V).

  Examples of the boron compound represented by the formula (VI) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, (N-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N , N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethyl Enyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and An example is tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Among these, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is most preferable.

  The boron compound is preferably a boron compound represented by the above formula (V) or the above formula (VI), particularly preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate or tri (n-butyl) ammonium. Tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

  In the polymerization of the diene compound, as a method of contacting the nickel compound with at least one of the organoaluminum compound and the boron compound, for example, they may be simply mixed or appropriately stirred. In this contact, the compound (monomer) represented by the formula (5) may be mixed or stirred together.

  When a polymerization catalyst is produced by bringing a nickel compound and an organoaluminum compound into contact, from the viewpoint of increasing the activity of the polymerization catalyst, as the organoaluminum compound, a cyclic aluminoxane represented by the above formula (II), the above formula ( The linear aluminoxane represented by III) or a combination thereof is preferred. From the same viewpoint, when the nickel compound, the organoaluminum compound, and the boron compound are brought into contact with each other to produce a polymerization catalyst, the organoaluminum compound represented by the above formula (I) is preferable as the organoaluminum compound.

  Although the usage-amount of an organoaluminum compound should just be able to produce | generate a catalyst, it is 0.1-10000 mol part per 1 mol part of nickel compounds, Preferably it is 5-2000 mol part. If the amount used is 0.1 mol parts or more, sufficient polymerization activity can be obtained, and if it is 10,000 mol parts or less, a polymer having a higher molecular weight can be obtained (for example, to an organoaluminum compound). And the higher activity of the polymerization catalyst can be obtained. The usage-amount of a boron compound is 0.01-100 mol part per mol part of transition metal compounds, for example, Preferably it is 0.5-10 mol part. When the amount used is 0.01 mol parts or more, it is advantageous in that the activity of the polymerization catalyst can be sufficiently obtained, and when it is less than 100 mol parts, the cost can be suppressed.

  Each of the nickel compound, organoaluminum compound and boron compound used in the polymerization of the diene compound may be used as a solution. Examples of the solvent for the solution include methylene chloride, chloroform, toluene, pentane, hexane, and heptane. Among these, methylene chloride, chloroform, or toluene is preferable.

  The density | concentration of a nickel compound solution is 0.01-500 micromol / L, for example, Preferably it is 0.05-100 micromol / L, More preferably, it is 0.05-50 micromol / L. The density | concentration of an organoaluminum compound solution is 0.01-10000 micromol / L in conversion of aluminum atom, for example, Preferably it is 0.1-5000 micromol / L, More preferably, it is 0.1-2000 micromol / L. The density | concentration of a boron compound solution is 0.01-500 micromol / L, for example, Preferably it is 0.05-200 micromol / L, More preferably, it is 0.05-100 micromol / L. By setting the concentration of the nickel compound solution to 0.01 μmol / L or more, the concentration of the organoaluminum compound solution is set to 0.01 μmol / L or more in terms of aluminum atoms, and the concentration of the boron compound solution is set to 0.01 μmol. By using / L or more, the amount of solvent used can be reduced, which is advantageous in terms of cost. Further, by setting the concentration of the nickel compound solution to 500 μmol / L or less, the concentration of the organoaluminum compound solution is set to 10000 μmol / L or less in terms of aluminum atoms, and the concentration of the boron compound solution is set to 500 μmol / L or less. By doing so, these compounds can be sufficiently dissolved, and precipitation of the compounds can be suppressed.

  The catalyst used in the polymerization of the diene compound may be combined with a carrier comprising an inorganic compound particulate material or an organic compound particulate material. Examples of the inorganic compound include silica gel and alumina. A styrene polymer can be illustrated as an organic compound.

[2-3. Polymerization method)
The polymerization method in the polymerization of the diene compound is not particularly limited. Examples of the polymerization method include batch type or continuous type gas phase polymerization method, bulk polymerization method, and solution polymerization method or slurry polymerization method using an appropriate polymerization solvent. The polymerization solvent is a solvent that does not deactivate the polymerization catalyst, and examples of the solvent include hydrocarbon solvents and halogenated solvents. Examples of the hydrocarbon solvent include benzene, toluene, pentane, hexane, heptane, and cyclohexane. Examples of the halogenated solvent include dichloromethane and chloroform.

  The polymerization temperature in the polymerization of the diene compound is, for example, −100 to 250 ° C., preferably −50 to 200 ° C. When the temperature is −100 ° C. or higher, the catalyst exhibits sufficient activity for the polymerization reaction, and when it is 250 ° C. or lower, a polymer having a higher molecular weight can be obtained, or the occurrence of side reactions can be suppressed. can do. Examples of this side reaction include an isomerization reaction.

  In the polymerization of the diene compound, a chain transfer agent may be used in order to adjust the molecular weight of the resulting polymer. Examples of the chain transfer agent include hydrogen.

  The polymerization time in the polymerization of the diene compound is, for example, 1 minute to 72 hours. When the polymerization time is 1 minute or longer, the polymer can be obtained in a sufficient yield, and by setting it to 72 hours or shorter, it is advantageous in that the production cost of the polymer can be suppressed.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail.

[Example 1]
Dibromo [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] nickel 7.2 mg (“Rekue ・(Synthesized with reference to “Recueil des Travaux Chimiques de Pays-Bas”, Vol. 113, 1994, page 88), 0.59 mL of toluene, 0.0962 g of 1,6-heptadiene (Manufactured by Wako Pure Chemical Industries, Ltd.) and 1.41 mL (manufactured by Tosoh Finechem) of MMAO (organoaluminum compound) toluene solution (MMAO-3A, Al: 6.6 wt%) were added and stirred at 0 ° C. for 18 hours. After the reaction, the reaction mixture was poured into methanol (about 50 mL) and filtered, and the obtained solid part was washed with methanol and vacuum dried to obtain 0.0470 g of the product (yield 48.9%). The number average molecular weight (M _n ) was 12900, and the molecular weight distribution (M _w / M _n ) was 1.20. The product contained a trans-1,2-cyclopentane structure (26%) and a cis-1,3-cyclohexane structure (74%). The product was a solid at room temperature, and a glass transition point was confirmed at 71 ° C. The 5% decomposition point (T _d ⁵ ) was 240 ° C. (TG analysis measurement).

The glass transition point was measured under the following conditions by differential scanning calorimetry (DSC) measurement using a model named SSC-5200 manufactured by Seiko Instruments Inc .:
Temperature rise: 25 ° C. to 150 ° C. (10 ° C./min) Hold for 5 minutes;
Cooling: 150 ° C to -60 ° C (20 ° C / min) Hold for 5 minutes;
Measurement: -60 ° C to 150 ° C (temperature increase at 10 ° C / min).

The above number average molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve was prepared using standard polystyrene:
Measuring instrument: manufactured by JASCO (Degasser: DG-980-50, pump: PU-980, autosampler: AS-950, column oven: CO-966, RI detector: RI-930, UV detector: UV-975 )
Column: Shodex-806L x 2 manufactured by Showa Denko KK Measurement temperature: 40 ° C
Solvent: Chloroform sample concentration: 1 mg / 1 ml.

That the obtained polymer has a repeating unit represented by formulas (3) and (4) is 15 to 15 in the spectrum of ¹³ C-NMR analysis using a model named LA-500 manufactured by JEOL Ltd. The signal group in the range of 60 ppm was confirmed by being able to be assigned as linear hydrocarbons and cyclic hydrocarbons of the structure represented by formulas (3) and (4):
Measuring solvent: chloroform-d ₁
Measurement temperature: room temperature Sample concentration: 50 mg / 0.5 ml
Reference material: chloroform-d ₁ (77 ppm).

The abundance ratio of the cyclic structure and its stereoregularity was determined by a method comprising the following procedure by ¹³ C-NMR analysis using a model named LA-500 manufactured by JEOL.
(1) A deuterated chloroform solution (concentration: 286 mg / mL) of the polymer was prepared.
(2) The ¹³ C-NMR spectrum of the solution was measured.
(3) Peak area of deuterated chloroform is 77 ppm, peak area appearing at 22.5 to 23.5 ppm of the spectrum (A _5C ) and peak area appearing at 23.8 to 24.8 ppm (A _5T ), 26 The peak area (A _6C ) appearing at 0.0-27.5 ppm and the peak area (A _6T ) appearing at 21.0-22.0 ppm were determined.
(4) Stereoregularity was calculated based on the following formula:
Trans-1,2-cyclopentane (%) = _100A5T / ( _A5T + _A5C + _A6T + _A6C )
Cis-1,2-cyclopentane (%) = 100A _5C / (A _5T + A _5C + A _6T + A _6C )
Trans-1,3-cyclohexane (%) = 100A _6T / (A _5T + A _5C + A _6T + A _6C )
Cis-1,3-cyclohexane (%) = 100A _6C / (A _5T + A _5C + A _6T + A _6C ).

[Example 2]
In Example 1, 7.2 mg of dibromo [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] nickel was added to dibromo [N, N '-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-dicyclohexylaniline-κN)] nickel 8.8 mg, except that 18 hours reaction time was changed to 3 hours Was carried out in the same manner as in Example 1 to obtain 0.0364 g of the product (yield 37.8%). The number average molecular weight (M _n ) was 9500, and the molecular weight distribution (M _w / M _n ) was 1.52. The product contained a trans-1,2-cyclopentane structure (28%) and a cis-1,3-cyclohexane structure (72%).

  The polymer according to the present invention can be suitably used for automobile parts, home appliance parts, optical materials and the like.

Claims (3)

The repeating unit represented by the following formula (1) and the repeating unit represented by the following formula (2), the repeating unit represented by the following formula (1) and the repeating unit represented by the following formula (2) The polymer whose quantity of the repeating unit represented by following formula (1) with respect to the total amount of is 70 mol% or more.

(In the above formula (1), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (2), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) The repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (3), and the repeating unit represented by the above formula (2) is represented by the following formula (4). The polymer according to claim 1, wherein

A diene compound represented by the following formula (5) is polymerized in the presence of a catalyst formed by contacting a nickel compound represented by the following formula (6) with at least one of an organoaluminum compound and a boron compound. And having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), represented by the repeating unit represented by the following formula (1) and the following formula (2): The manufacturing method which manufactures the polymer whose quantity of the repeating unit represented by following formula (1) is 70 mol% or more with respect to the total amount of the repeating unit.

(In the above formula (5), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (6), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other; ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, an aralkyloxy group, or an aryloxy group, and R ^{5 to} R ⁸ represent Each independently represents a hydrocarbon group having 3 to 30 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, Represents an aralkyloxy group, an aryloxy group, an amino group, an amide group, an imide group, or a hydrocarbon thio group)

(In the above formula (1), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

(In the above formula (2), A ^{1 to} A ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)