JP2012031334A - Conjugated diene-alpha olefin copolymer, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conjugated diene-α-olefin copolymer useful especially as an elastomer and a method of manufacturing the same.SOLUTION: The conjugated diene-α-olefin copolymer comprises a conjugated diene and a 4-8C α-olefin, wherein the polystyrene conversion weight-average molecular weight by a GPC (gel permeation chromatography) is at least 90,000.

Description

  The present invention relates to a conjugated diene / α-olefin copolymer having high utility value and a method for producing a conjugated diene / α-olefin copolymer using a specific transition metal complex catalyst.

  Conventionally, conjugated diene / α-olefin copolymers have been used in a wide range of fields while imparting physical properties according to various uses, and in order to obtain such conjugated diene / α-olefin copolymers, a production method is available. Numerous studies have also been made. Under these circumstances, for example, Patent Documents 1 to 3 disclose a method for producing a conjugated diene / α-olefin copolymer using a specific catalyst, and a copolymer having a specific structure is obtained. .

JP-A-48-74588 Special table 2003-532766 gazette Special table 2007-501881

  However, in any of the above production methods, a copolymer having a sufficiently high molecular weight cannot always be obtained, and a copolymer having good processability has been desired. In addition, there is still room for improvement in order to obtain a conjugated diene / α-olefin copolymer particularly useful as an elastomer.

  Therefore, an object of the present invention is to provide a conjugated diene / α-olefin copolymer particularly useful as an elastomer and a production method for obtaining the same.

  In order to solve the above-mentioned problems, the present inventors have used a high molecular weight conjugated diene / α-olefin copolymer and a conjugated diene / α-olefin copolymer having high utility value by using a specific transition metal complex catalyst. The present inventors have found a production method capable of obtaining the present invention and completed the present invention.

  That is, the conjugated diene / α-olefin copolymer of the present invention comprises a conjugated diene and an α-olefin having 4 to 8 carbon atoms, and has a polystyrene-reduced weight average molecular weight of 90000 or more by GPC (gel permeation chromatography). It is characterized by that.

  The α-olefin is more preferably 1-butene.

  The conjugated diene preferably has 4 to 8 carbon atoms, more preferably butadiene or isoprene.

  In the method for producing a conjugated diene / α-olefin copolymer of the present invention, M = Q bond (M represents a transition metal of groups IV to VI of the periodic table, and Q represents an oxygen atom or a nitrogen atom. When Q is a nitrogen atom, the nitrogen atom further binds to an element other than M.) and at least one ligand selected from the group consisting of a hydrogen atom, a halogen atom, and an organic compound residue A conjugated diene / α-olefin copolymer composed of a conjugated diene and an α-olefin having 4 to 8 carbon atoms is obtained using a transition metal complex catalyst having the following.

（式（Ｉ）中、Ｍは周期律表ＩＶ〜ＶＩ族の遷移金属を示し、Ｑは酸素原子又は窒素原子を示す。Ａ及びＢは同一であっても異なっていてもよく、水素原子又は有機化合物残基を示し、ここで、Ａの一部とＢの一部とが環を形成していてもよい。Ｘはハロゲン原子を示し、ｘは０〜３の整数を示し、ｙは０〜３の整数を示す。但し、１≦ｘ＋ｙ≦３である。）で表されるのが望ましい。 The transition metal complex catalyst is represented by the following formula (I):

(In formula (I), M represents a transition metal of groups IV to VI of the periodic table, Q represents an oxygen atom or a nitrogen atom. A and B may be the same or different, and may be a hydrogen atom or An organic compound residue, wherein a part of A and a part of B may form a ring, X represents a halogen atom, x represents an integer of 0 to 3, and y represents 0 Represents an integer of ˜3, where 1 ≦ x + y ≦ 3).

（式（ＩＩ）中、Ｍは周期律表ＩＶ〜ＶＩ族の遷移金属を示し、Ｑは酸素原子又は窒素原子を示す。Ｒ^１及びＲ^２は同一であっても異なっていてもよく、炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基を示し、ここでＲ^１の一部とＲ^２の一部とが環を形成していてもよい。Ｘはハロゲン原子を示し、ｘは０〜３の整数を示し、ｙは０〜３の整数を示す。但し、１≦ｘ＋ｙ≦３である。）で表されるのが望ましい。 The transition metal complex catalyst is represented by the following formula (II):

(In formula (II), M represents a transition metal of groups IV to VI of the periodic table, Q represents an oxygen atom or a nitrogen atom. R ¹ and R ² may be the same or different, and An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, wherein a part of R ^{1 and} a part of R ² may form a ring, X represents a halogen atom, x represents an integer of 0 to 3, and y represents an integer of 0 to 3, provided that 1 ≦ x + y ≦ 3.

（式（ＩＩＩ）中、Ｍは周期律表ＩＶ〜ＶＩ族の遷移金属を示し、Ｑは酸素原子又は窒素原子を示す。Ｒ^３〜Ｒ^８は同一であっても異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を示す。Ｘは塩素原子又は臭素原子を示し、ｘは０〜３の整数を示し、ｙは０〜３の整数を示す。但し、１≦ｘ＋ｙ≦３である。ｍは１〜５の整数を示し、ｎは１〜５の整数を示す。）で表されるのが望ましい。 The transition metal complex catalyst is represented by the following formula (III);

(In the formula (III), M represents a transition metal of groups IV to VI in the periodic table, Q represents an oxygen atom or a nitrogen atom. R ^{3 to} R ⁸ may be the same or different, and Represents an atom or an alkyl group having 1 to 8 carbon atoms, X represents a chlorine atom or a bromine atom, x represents an integer of 0 to 3, and y represents an integer of 0 to 3. However, 1 ≦ x + y ≦ 3 It is desirable that m represents an integer of 1 to 5 and n represents an integer of 1 to 5).

（式（Ｉ）中、Ｒ^１２は水素原子または炭素数１〜４のアルキル基を示し、Ｒ^１３は水素原子または炭素数１〜４のアルキル基を示し、Ｒ^１４は炭素数１〜８のアルキル基を示し、Ｘは塩素原子または臭素原子を示す。）で表されるバナジウムアルコキシハロゲン化合物であるのが望ましい。 As the transition metal complex catalyst, the following formula (IV):

(In the formula (I), R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ has 1 to 8 carbon atoms. It is preferably a vanadium alkoxy halogen compound represented by the following formula: X represents an alkyl group, and X represents a chlorine atom or a bromine atom.

The transition metal complex catalyst is preferably vanadyl-di- (2,2-dimethylpropoxy) -chloride.
Further, it is desirable to use an organoaluminum compound as a cocatalyst, and the organoaluminum compound is preferably triisobutylaluminum.
Furthermore, it is desirable to use n-hexane as a solvent.
In the conjugated diene / α-olefin copolymer, the content of structural units derived from the α-olefin is preferably 20 to 80 mol%.

  The α-olefin is more preferably 1-butene.

  The conjugated diene preferably has 4 to 8 carbon atoms, more preferably butadiene.

  Since the conjugated diene / α-olefin copolymer of the present invention has a polystyrene-equivalent weight average molecular weight of 90000 or more, it has good processability and can exhibit viscoelasticity particularly suitable for kneading, and can be used as an elastomer. Can be used effectively.

  According to the method for producing a conjugated diene / α-olefin copolymer of the present invention, a conjugated diene / α-olefin copolymer having a high molecular weight is obtained while sufficiently increasing the content of structural units derived from the α-olefin. Can be easily obtained.

3 is a ¹³ C-NMR spectrum chart of Example copolymer 1. FIG. 2 is a ¹ H-NMR spectrum chart of Example copolymer 1. FIG.

Hereinafter, the present invention will be specifically described.
The method for producing a conjugated diene / α-olefin copolymer of the present invention comprises a conjugated diene and an α-olefin having 4 to 8 carbon atoms, and has a polystyrene-reduced weight average molecular weight of 90000 or more by GPC (gel permeation chromatography). It is characterized by being.
The polystyrene-reduced weight average molecular weight is preferably 150,000 or more, more preferably 250,000 or more.

  The conjugated diene / α-olefin copolymer of the present invention is a copolymer obtained by copolymerizing a conjugated diene and an α-olefin having 4 to 8 carbon atoms as a monomer.

  The conjugated diene is preferably a conjugated diene having 4 to 12 carbon atoms, more preferably a conjugated diene having 4 to 8 carbon atoms, specifically 1,3-butadiene, isoprene, 2-ethyl-1,3- Butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-butadiene, 2-methyl-1,3-hexadiene 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, 2,3-dimethyl-1,3-decadiene, ethylidene norbornene, vinyl norbornene (5-vinylbicyclo [2.2 .1] hept-2-ene), dicyclopentadiene, 2-methyl-1,4-hexadiene, 2-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8- Examples thereof include methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene. Of these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable. These may be used alone or in combination of two or more.

  The α-olefin having 4 to 8 carbon atoms may be linear or branched. Specifically, 1-butene, 3-methyl-1-butene, 2-methyl-1 -Propene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,4-dimethyl-1-pentene, 1-heptene, 1-octene, vinylcyclohexene . These may be used alone or in combination of two or more. Of these, 1-butene is more preferable. These may be used alone or in combination of two or more.

  In the conjugated diene / α-olefin copolymer, the content of structural units derived from the α-olefin is usually 20 to 80 mol%. Thus, by increasing the content of the structural unit derived from the α-olefin, a copolymer having a higher molecular weight and easy kneading as an elastomer can be obtained.

  In the method for producing a conjugated diene / α-olefin copolymer of the present invention, M = Q bond (M represents a transition metal of groups IV to VI of the periodic table, and Q represents an oxygen atom or a nitrogen atom. When Q is a nitrogen atom, the nitrogen atom further binds to an element other than M.) and at least one ligand selected from the group consisting of a hydrogen atom, a halogen atom, and an organic compound residue A conjugated diene / α-olefin copolymer composed of a conjugated diene and an α-olefin having 4 to 8 carbon atoms is obtained using a transition metal complex catalyst having the following.

In the production method of the present invention, a transition metal complex catalyst component having M = Q bond as a catalyst component and having at least one ligand selected from the group consisting of a hydrogen atom, a halogen atom, and an organic compound residue Is used.
Here, M represents a transition metal of groups IV to VI of the periodic table, and Q represents an oxygen atom or a nitrogen atom. However, when Q is a nitrogen atom, the nitrogen atom is further bonded to an element other than M.

  Examples of the transition metals of groups IV to VI of the periodic table include titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum, and tungsten, and vanadium is particularly preferable.

  Examples of the ligand include a hydrogen atom or a halogen atom which is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and an organic compound residue such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group. Group, sec-butoxy group, aliphatic alkoxy group such as tert-butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group, thiomethoxy group, thioethoxy group, thiopropoxy group, thio n- Butoxy group, thioisobutoxy group, thiosec-butoxy group, thioter -Aliphatic thiolate group such as butoxy group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert Aryl such as -butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group Thiolate group; aliphatic amide group such as dimethylamide group, diethylamide group, diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6- Dineopentylphenylamide group, 2-tert-butyl-6-i Arylamide groups such as propylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; Bistrialkylsilylamide group such as trimethylsilylamide group, trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, methyl group, ethyl group , N-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group, octyl group and the like linear or branched aliphatic hydrocarbon group; phenyl Group, tolyl Group, aromatic hydrocarbon group such as naphthyl group; aralkyl group such as benzyl group, etc., hydrocarbon group containing silicon atom such as trimethylsilylmethyl group, bistrimethylsilylmethyl group and the like.

  Further, aldehyde residues such as salicylaldehyde, 2-hydroxy-1-naphthalaldehyde, 2-hydroxy-3-naphthalaldehyde, 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone Hydroxyphenone residues such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone and other diketones residues, isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid , Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bipallic acid, versatic acid (mixture of isomers of C10 monocarboxylic acid sold by Shell Chemical) Carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid, hexanethiolic acid, 2,2-dimethylbutanethioic acid, decanthioic acid, thiobenzoic acid, etc. , Dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate, dioleyl phosphate, phosphoric acid Diphenyl, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphate (1-methylheptyl) (2-ethylhexyl), Phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid Butyl, 2-ethylhexylphosphonic acid mono-2-ethylhexyl, phenylphosphonic acid mono-2-ethylhexyl, 2-ethylhexylphosphonic acid mono-p-nonylphenyl, phosphonic acid mono-2-ethylhexyl, phosphonic acid mono-1-methylheptyl , Mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p -Nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2- D Examples also include organic compound residues such as organic phosphoric acid residues such as tilhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid and p-nonylphenylphosphinic acid. These ligands may be used alone or in combination of two or more as necessary.

More specifically, examples of the transition metal complex catalyst component include those represented by the following formula (I).

  In formula (I), M and Q are as defined above. A and B may be the same or different and each represents a hydrogen atom or an organic compound residue, and a part of A and a part of B may form a ring. The organic compound residue is as defined above. X represents a halogen atom which is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among them, a chlorine atom or a bromine atom is preferable. x represents an integer of 0 to 3, and y represents an integer of 0 to 3. However, 1 ≦ x + y ≦ 3.

Moreover, the transition metal complex catalyst component represented by following formula (II) is mentioned.

In formula (II), M, Q, X, x, and y are as defined above. R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, wherein a part of R ¹ and ^one of R ² The part may form a ring.

Furthermore, the transition metal complex catalyst component represented by following formula (III) is mentioned.

In formula (III), M, Q, X, x, and y are as defined above. R ^{3 to} R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m represents an integer of 1 to 5, and n represents an integer of 1 to 5.

Among the transition metal complex catalyst components represented by the above formulas (I) to (III), vanadyl alkoxy halogen compounds represented by the following formula (IV) are preferable.

In the formula (IV), R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ represents an alkyl having 1 to 8 carbon atoms. Represents a group, and X represents a chlorine atom or a bromine atom. By using such a transition metal complex catalyst component together with a co-catalyst component to be described later, more sufficient polymerization activity can be ensured.

  More specifically, examples of the vanadyl alkoxy halogen compound include vanadyl-di- (neopentyloxy) -oxychloride, vanadyl-di- (isobutoxy) -oxychloride, vanadyl-di- (2-ethylhexyloxy). Oxychloride, vanadyl-di- (2,2-dimethylpropoxy) -chloride, vanadyl- (neopentyloxybutoxy) -oxychloride, vanadyl- (neopentyloxy-octyloxy) -oxychloride, vanadyl-2-ethylhexyl And oxy-butoxy-oxychloride. Of these, vanadyl-di- (2,2-dimethylpropoxy) -chloride is preferred.

In the production method of the present invention, an organoaluminum compound is used as a promoter component, and specifically, AlR ⁹ R ¹⁰ R ¹¹ or aluminoxane is preferable. Here, R ⁹ and R ¹⁰ may be the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms.

More specifically, examples of the organoaluminum compound represented by AlR ⁹ R ¹⁰ R ¹¹ include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, and triisobutyl. Aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, hydrogenation Diisobutylaluminum, hydrogenated dihexylaluminum, hydrogenated diisohexylaluminum, hydrogenated dioctylaluminum, hydrogenated diisooctylaluminum; Aluminum dihydride, n- propyl aluminum dihydride, isobutyl aluminum dihydride, and the like. These may be used alone or in combination of two or more. Of these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable.

The aluminoxane used as the organoaluminum compound is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. More specifically, the aluminoxane is represented by the general formula (—Al (R ⁰ ) O— ) A chain aluminoxane represented by _n or a cyclic aluminoxane. Here, R ⁰ is a hydrocarbon group having 1 to 10 carbon atoms, including a part of which is substituted with a halogen atom and / or an alkoxy group. n is the degree of polymerization and is 5 or more, preferably 10 or more. Specific examples of R ⁰ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among them, a methyl group is preferable. Examples of the organoaluminum compound used as a raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. Of these, trimethylaluminum is most preferable. An aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can also be suitably used.

  The transition metal complex catalyst component is usually added in an amount of 0.1 to 3 mmol, preferably 0.1 to 1.5 mmol per 100 g of the total amount of α-olefin and conjugated diene. The molar ratio between the organoaluminum compound as the promoter component and the transition metal complex catalyst component is usually 20: 1 to 2: 1, preferably 10: 1 to 5: 1.

  The polymerization reaction includes at least one selected from the group consisting of saturated alicyclic hydrocarbons, aromatic hydrocarbons, and halogen derivatives thereof, in the presence of the transition metal complex catalyst component and the promoter component, containing n-hexane. In a solvent containing By containing n-hexane as a solvent, an α-olefin-conjugated diene copolymer having a larger molecular weight can be obtained.

  The solvent contains at least n-hexane, and 0 mass of at least one selected from the group consisting of saturated alicyclic hydrocarbons, aromatic hydrocarbons, and halogen derivatives thereof in 100 mass% of the total amount of the solvent. % To 50% by mass or less, preferably 5 to 40% by mass, more preferably 10 to 30% by mass. Polymerization using not only n-hexane but also a saturated alicyclic hydrocarbon, aromatic hydrocarbon or halogen derivative thereof alone or in a mixture of two or more and containing a specific amount thereof. By performing the step, it is possible to effectively suppress the amount of gel that is likely to occur when polymerization is performed using a solvent containing n-hexane under low temperature conditions.

  The saturated alicyclic hydrocarbon is preferably a saturated alicyclic hydrocarbon having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, specifically, for example, cyclopentane, Examples include cyclohexane, methylcyclopentane, cycloheptane, cyclooctane, cyclononane, and cyclodecane. Of these, cyclohexane is preferable. As the aromatic hydrocarbon, an aromatic hydrocarbon having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms is preferable. Specific examples thereof include benzene, toluene, xylene, and ethylbenzene. , Diethylbenzene, and ethylmethylbenzene. Of these, toluene, benzene, and xylene are preferable. Moreover, halogen derivatives of these saturated alicyclic hydrocarbons or aromatic hydrocarbons, for example, chlorinated saturated alicyclic hydrocarbons or aromatic hydrocarbons, specifically, chlorobenzene or dichloromethane can also be used. In addition, it is desirable to use the said saturated alicyclic hydrocarbon from a viewpoint of suppressing generation | occurrence | production of gel more effectively.

  As described above, the solvent used in the production method of the present invention includes at least n-hexane and is selected from the group consisting of a specific amount of saturated alicyclic hydrocarbon, aromatic hydrocarbon and halogen derivatives thereof. It is sufficient that it contains at least one kind, and the remainder contains other solvents, for example, aliphatic hydrocarbons other than n-hexane such as pentane and heptane, etc. within the range not impairing the effects of the present invention. May be.

  In the polymerization reaction, a mixture obtained by adding the α-olefin and the conjugated diene monomer to the solvent is preferably polymerized at a temperature of −78 ° C. to 0 ° C., more preferably −78 to −30 ° C., most preferably −78. It is good to cool so that it may become less than ~ -50 degreeC. By lowering the polymerization temperature within the above range, the molecular weight of the resulting copolymer can be further increased. Next, while maintaining this temperature, the transition metal complex catalyst component and the promoter component are added to the mixture to initiate polymerization. The order of addition of the transition metal complex catalyst component and the promoter component is not particularly limited. The polymerization pressure is not particularly limited, and the polymerization can be performed under normal pressure.

  After the polymerization reaction is completed, the transition metal complex catalyst and, if necessary, the cocatalyst are deactivated by adding an amine such as triethylamine, an alcohol such as ethanol, or a carboxylic acid such as formic acid. The product can be isolated by precipitation or stripping after the addition of a stabilizer such as 2,6-di-t-butylmethylphenol, washed and dried to obtain the desired copolymer. Such a polymerization reaction may be either a batch type or a continuous type.

  Moreover, as a suitable rubber material by adding a filler such as carbon black, silica, calcium carbonate, a crosslinking agent such as sulfur, a crosslinking accelerator, a crosslinking aid, etc., kneading, molding and then crosslinking by heating. Available. In particular, it is optimally used for automobile parts, especially tire members.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The physical properties of the copolymer were measured according to the following method.

<< Weight average molecular weight Mw >>
The polystyrene-converted weight average molecular weight (Mw) measured by GPC of the copolymers obtained in Examples and Comparative Examples was measured under the following conditions using GPC (manufactured by VISCOTEK, TDA).
Column: Tosoh Co., Ltd., two columns GMHHXL are used in series Mobile phase: Tetrahydrofuran

<Mooney viscosity>
It measured at 100 degreeC based on JISK6300-1994.

<Processability>
The adhesiveness to the roll was evaluated based on the following criteria under a 3-inch roll, 65 ° C., and a roll kneading condition of 16 to 18 rpm (rotation number).
A: The copolymer can be kneaded without being in close contact with the roll. ○: The copolymer is in close contact with each other but can be kneaded. X: Since the copolymer is in a liquid state, roll kneading is impossible.

[Example copolymer 1]
A mixture of 14.5 g n-hexane, 13.5 g butadiene and 1.5 g 1-butene (9.3: 1 molar ratio) was cooled to −78 ° C. in the presence of nitrogen. 1 mmol of triisobutylaluminum and 0.13 mmol of vanadyl-di- (2,2-dimethylpropoxy) -chloride were added to initiate the polymerization reaction under normal pressure. The reaction temperature was maintained at −78 ° C. by external cooling. After a reaction time of 12 hours, the polymerization was stopped by adding 8% by volume of isopropanol or ethanol. The obtained product was precipitated in isopropanol or ethanol, washed, and then dried at 50 ° C. under reduced pressure to obtain a butene-butadiene copolymer example copolymer 1. The yield of Example copolymer 1 was 2.1 g, the polystyrene-equivalent weight average molecular weight was 257000 (molecular weight distribution 2.30), and the Mooney viscosity was 25.5. 1 is a ¹³ C-NMR spectrum chart (room temperature, chloroform-d) of Example copolymer 1, and FIG. 2 is a ¹ H-NMR spectrum chart (room temperature, chloroform of Example copolymer 1). -D).

[Example copolymer 2]
Example copolymer 2 was obtained in the same manner as Example copolymer 1, except that 28 g of n-hexane, 7 g of butadiene, and 3 g of 1-butene (molar ratio 2.4: 1) were used. The yield of Example Copolymer 2 was 2.0 g, the weight average molecular weight in terms of polystyrene was 195000 (molecular weight distribution 1.91), and the Mooney viscosity was 19.0.

[Example copolymer 3]
Example copolymer 3 was obtained in the same manner as Example copolymer 1 except that 41 g of n-hexane, 8 g of butadiene, and 2 g of 1-butene (molar ratio 4.2: 1) were used. The yield of Example copolymer 3 was 2.6 g, the polystyrene-equivalent weight average molecular weight was 173000 (molecular weight distribution 1.98), and the Mooney viscosity was 18.5.

[Comparative Example Copolymer]
A comparative example copolymer was obtained in the same manner as Example copolymer 1 except that 28 g of toluene, 4 g of butadiene, and 6 g of 1-butene (molar ratio 0.7: 1) were used. The yield of the comparative copolymer was 1.7 g, the polystyrene equivalent weight average molecular weight was 88000 (molecular weight distribution 1.76), and the Mooney viscosity was 9.0.

  Examples Copolymers 1 to 3 were able to express viscoelasticity suitable for kneading with respect to the comparative copolymer, and were excellent in processability.

Claims (17)

A conjugated diene / α-olefin copolymer comprising a conjugated diene and an α-olefin having 4 to 8 carbon atoms,
A conjugated diene / α-olefin copolymer having a polystyrene-reduced weight average molecular weight of 90000 or more by GPC (gel permeation chromatography).   The conjugated diene / α-olefin copolymer according to claim 1, wherein the α-olefin is 1-butene.   The conjugated diene / α-olefin copolymer according to claim 1 or 2, wherein the conjugated diene is a copolymer having 4 to 8 carbon atoms.   The conjugated diene / α-olefin copolymer according to claim 1, wherein the conjugated diene is butadiene or isoprene.   M = Q bond (M represents a transition metal of groups IV to VI of the periodic table, Q represents an oxygen atom or a nitrogen atom. However, when Q is a nitrogen atom, the nitrogen atom further binds to an element other than M. And a transition metal complex catalyst having at least one ligand selected from the group consisting of a hydrogen atom, a halogen atom, and an organic compound residue, and a conjugated diene and a carbon number of 4 to 8 A method for producing a conjugated diene / α-olefin copolymer comprising obtaining a conjugated diene / α-olefin copolymer comprising an α-olefin. The transition metal complex catalyst is represented by the following formula (I):

(In formula (I), M represents a transition metal of groups IV to VI of the periodic table, Q represents an oxygen atom or a nitrogen atom. A and B may be the same or different, and may be a hydrogen atom or An organic compound residue, wherein a part of A and a part of B may form a ring, X represents a halogen atom, x represents an integer of 0 to 3, and y represents 0 6 represents an integer of ˜3, where 1 ≦ x + y ≦ 3.) The method for producing a conjugated diene / α-olefin copolymer according to claim 5. The transition metal complex catalyst is represented by the following formula (II):

(In formula (II), M represents a transition metal of groups IV to VI of the periodic table, Q represents an oxygen atom or a nitrogen atom. R ¹ and R ² may be the same or different, and An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, wherein a part of R ^{1 and} a part of R ² may form a ring, X represents a halogen atom, x represents an integer of 0 to 3, and y represents an integer of 0 to 3, provided that 1 ≦ x + y ≦ 3.) The conjugated diene / α according to claim 6, -Manufacturing method of an olefin copolymer. The transition metal complex catalyst is represented by the following formula (III);

(In the formula (III), M represents a transition metal of groups IV to VI in the periodic table, Q represents an oxygen atom or a nitrogen atom. R ^{3 to} R ⁸ may be the same or different, and Represents an atom or an alkyl group having 1 to 8 carbon atoms, X represents a chlorine atom or a bromine atom, x represents an integer of 0 to 3, and y represents an integer of 0 to 3. However, 1 ≦ x + y ≦ 3 The conjugated diene / α-olefin copolymer according to claim 6 or 7, wherein m represents an integer of 1 to 5, and n represents an integer of 1 to 5. Manufacturing method. As the transition metal complex catalyst, the following formula (IV):

(In the formula (I), R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ has 1 to 8 carbon atoms. The conjugated diene / α-olefin copolymer according to claim 6, wherein the compound is a vanadium alkoxy halogen compound represented by the following formula: Manufacturing method of coalescence.   The conjugated diene / α-olefin copolymer according to any one of claims 5 to 9, wherein the transition metal complex catalyst is vanadyl-di- (2,2-dimethylpropoxy) -chloride. Method. As a further ^cocatalyst, AlR ^{9 R} 10 ^{R 11} (wherein, ^{R 9} and ^{R 10} may be the same or different and a hydrocarbon group or a hydrogen atom having 1 to 10 carbon ^{atoms, R 11} is The method for producing a conjugated diene / α-olefin copolymer according to any one of claims 5 to 10, wherein a hydrocarbon group having 1 to 10 carbon atoms) or aluminoxane is used.   The method for producing a conjugated diene / α-olefin copolymer according to claim 11, wherein the promoter is triisobutylaluminum.   The method for producing a conjugated diene / α-olefin copolymer according to any one of claims 5 to 12, wherein n-hexane is used as a solvent.   The conjugated diene / α-olefin copolymer according to claim 5, wherein the conjugated diene / α-olefin copolymer has a content of structural units derived from the α-olefin of 20 to 80 mol%. A method for producing an olefin copolymer.   The method for producing a conjugated diene / α-olefin copolymer according to claim 5, wherein the α-olefin is 1-butene.   The method for producing a conjugated diene / α-olefin copolymer according to any one of claims 5 to 15, wherein the conjugated diene has 4 to 8 carbon atoms.   The method for producing a conjugated diene / α-olefin copolymer according to any one of claims 5 to 16, wherein the conjugated diene is butadiene or isoprene.

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