JP5539808B2 - Process for producing 1,3-butadiene / 1-butene copolymer and 1,3-butadiene / 1-butene copolymer obtained therefrom - Google Patents

Description

  The present invention relates to a process for producing a 1,3-butadiene / 1-butene copolymer using a specific transition metal complex catalyst, and a 1,3-butadiene / 1-butene copolymer having high utility value obtained therefrom. .

  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 employing a specific catalyst, such as butene-butadiene copolymers each having a specific structure. Has been obtained.

  In general, ethylene and propylene, which are typical monomers used to produce such copolymers, pyrolyze raw naphtha, etc., separate, recover, and purify from cracked gas, and fluid contact in refineries. It is produced by separation, recovery and purification from cracked (FCC) gas, butene is produced from the FCC gas, and butadiene is produced by solvent extraction from the C4 fraction in the naphtha cracked gas.

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 is not necessarily obtained. In order to obtain a 1,3-butadiene / 1-butene copolymer particularly useful as an elastomer. There is still room for improvement. In addition, in order to obtain a monomer used for polymerization, it has already been forced to go through many steps until the start of polymerization, but there is still nothing to do with reducing the number of steps as a whole copolymer production method. Not considered.

Accordingly, the present invention provides a method for producing a 1,3-butadiene / 1-butene copolymer having a high molecular weight and a 1,3-butadiene / 1-butene copolymer obtained therefrom, which can effectively reduce the production process. The purpose is to provide.

In order to solve the above problems, the present inventors use a specific transition metal complex catalyst, which has a high molecular weight with high utility value even when an unpurified monomer mixed solution is directly used as a raw material. The inventors have found a production method capable of obtaining a 3-butadiene / 1-butene copolymer and have completed the present invention.

That is, the method for producing the 1,3-butadiene / 1-butene copolymer of the present invention includes:
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, 1,3-butadiene , 1-butene 1, having a polystyrene equivalent weight average molecular weight of 90,000 or more by GPC (gel permeation chromatography), selectively from an unpurified monomer mixed solution containing isobutene, cis-2-butene and trans-2-butene A 3-butadiene / 1-butene copolymer is obtained.

（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（ＩＶ）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触媒であるのが望ましい。 The transition metal complex catalyst is represented by the following formula (IV):

(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 has 1 to 8 carbon atoms. An alkyl group, and X is a chlorine atom or a bromine atom).

The transition metal complex catalyst is preferably vanadyl-di- (2,2-dimethylpropoxy) -chloride.
Further, as a co-catalyst, AlR ⁹ R ¹⁰ R ¹¹ (wherein R ⁹ and R ¹⁰ may be the same or different and each represents a C 1-10 hydrocarbon group or a hydrogen atom; ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms) or aluminoxane, and the promoter is preferably triisobutylaluminum.

In the monomer mixed solution, the butene is preferably contained in an amount of 1 to 300 mol% with respect to the 1,3-butadiene, and the butene in the monomer mixed solution contains 1-butene. In addition, it may contain at least one selected from the group consisting of 1-butene, cis-2-butene, trans-2-butene, and isobutene.
The monomer mixed solution is preferably a C4 fraction.

Furthermore, in the 1,3-butadiene / 1-butene copolymer, the content of structural units derived from 1-butene is preferably 20 to 80 mol% .

  According to the present invention, in the method for producing a 1,3-butadiene / 1-butene copolymer, the entire production process can be simplified, and 1,3-butadiene / 1-butene having a high molecular weight can be achieved. A copolymer can be easily obtained, and such a copolymer is very useful because it can be kneaded and is particularly suitable for use as an elastomer.

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 the 1,3-butadiene / 1-butene copolymer of the present invention includes:
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, 1,3-butadiene , 1-butene 1, having a polystyrene equivalent weight average molecular weight of 90,000 or more by GPC (gel permeation chromatography), selectively from an unpurified monomer mixed solution containing isobutene, cis-2-butene and trans-2-butene It is characterized by obtaining a 3-butadiene / 1-butene copolymer.

  The 1,3-butadiene / 1-butene copolymer obtained by the production method of the present invention is a copolymer obtained by copolymerizing 1,3-butadiene and 1-butene as monomers. .

  In the 1,3-butadiene / 1-butene copolymer, the content of structural units derived from 1-butene is usually preferably 20 to 80 mol%. Thus, by increasing the content of the structural unit derived from 1-butene, a copolymer having a higher molecular weight and easy kneading as an elastomer can be obtained.

  In the production method of the present invention, the 1,3-butadiene / 1-butene copolymer is selectively obtained from an unpurified monomer mixed solution containing butadiene and butene. Therefore, it is not necessary to purify in order to use 1,3-butadiene and 1-butene as monomers in advance, and it is possible to utilize the unrefined fraction by-produced during the essential oil process as it is. It can greatly contribute to the reduction.

  The monomer mixed solution only needs to contain at least 1,3-butadiene and 1-butene, and may contain butane, isobutane, vinylacetylene, ethylacetylene, and the like. An organic solvent is used as the solvent. Examples of the organic solvent include pentane, hexane, heptane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, ethylmethylbenzene, and chlorobenzene. These may be used alone or in combination of two or more.

  The butene contained in the monomer mixed solution is preferably contained in an amount of 1 to 300 mol% with respect to 1,3-butadiene.

  The butene contained in the monomer mixed solution may contain 1-butene or at least one selected from the group consisting of cis-2-butene, trans-2-butene, and isobutene. Good. Even if such butene contains not only 1-butene but also a plurality of butenes, it is possible to selectively copolymerize 1-butene by the action of a transition metal complex catalyst described later, For example, even a C4 fraction as shown in Table 1 that is by-produced by FCC can be suitably used simply by preparing a solution using the solvent. Therefore, since it is not necessary to purify 1-butene in advance and a 1,3-butadiene / 1-butene copolymer can be obtained directly from this, it can greatly contribute to the reduction of the process and cost reduction. It can also contribute to the effective use of resources.

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 (also referred to as vanadium catalysts) 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 1,3-butadiene / 1-butene copolymer. 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 is performed in the presence of the transition metal complex catalyst component and the promoter component in a solvent containing at least one selected from the group consisting of saturated alicyclic hydrocarbons, aromatic hydrocarbons, and halogen derivatives thereof. Is called.

  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 only needs to contain at least one selected from the group consisting of saturated alicyclic hydrocarbons, aromatic hydrocarbons and halogen derivatives thereof, and the balance. May contain other solvents, for example, aliphatic hydrocarbons such as n-hexane, pentane, and heptane, as long as the effects of the present invention are not impaired.

  In the polymerization reaction, a solution containing the 1,3-butadiene and 1,3-butadiene / 1-butene monomer is preferably polymerized at a temperature of −78 ° C. to 0 ° C., more preferably −78 to −30 ° C., Most preferably, it is good to cool so that it may become -78--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.

  The 1,3-butadiene / 1-butene copolymer obtained by the production method of the present invention is characterized by a very high molecular weight. Specifically, the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) is 90,000 or more. Therefore, viscoelasticity suitable for kneading can be expressed, and it can be effectively used as an elastomer. 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

[Example copolymer 1]
A mixture of 64 g toluene, 4 g 1,3-butadiene and 2 g 1-butene (molar ratio 2: 1), 2 g isobutene, 1 g cis-2-butene, 1 g trans-2-butene is present in the presence of nitrogen. Cool down to -78 ° C. 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 Example Copolymer 1 of 1,3-butadiene / 1-butene copolymer. The yield of Example copolymer 1 was 1.0 g, and the polystyrene-equivalent weight average molecular weight was 103000 (molecular weight distribution 1.82). 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]
10 g cyclohexane, 15 g toluene, 5 g 1,3-butadiene and 2 g 1-butene (molar ratio 2.4: 1), 2.5 g isobutene, 0.25 g cis-2-butene, 1 g trans Example copolymer 2 was obtained in the same manner as Example copolymer 1, except that a mixture of 2-butene was used. The yield of Example copolymer 2 was 1.7 g, and the weight average molecular weight in terms of polystyrene was 125000 (molecular weight distribution 1.82).

[ Reference Example Copolymer 3]
A mixture of 64 g toluene, 4 g 1,3-butadiene and 4 g 1-butene (1: 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 Reference Example Copolymer 3 of 1,3-butadiene / 1-butene copolymer. The yield of Reference Example copolymer 3 was 4.6 g, and the polystyrene-equivalent weight average molecular weight was 101000 (molecular weight distribution 1.96).

Claims (12)

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, 1,3-butadiene , 1-butene 1,3-Butadiene 1-, which has a polystyrene-reduced weight average molecular weight of 90,000 or more by GPC (gel permeation chromatography), selectively from a mixed solution containing , isobutene, cis-2-butene and trans-2-butene A method for producing a 1,3-butadiene / 1-butene copolymer, comprising obtaining a butene copolymer. 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 It represents the integer of -3, However, It is 1 <= x + y <= 3.) The manufacturing method of the 1, 3- butadiene * 1-butene copolymer of Claim 1 characterized by the above-mentioned. 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, 3. x represents an integer of 0 to 3, and y represents an integer of 0 to 3, provided that 1 ≦ x + y ≦ 3). A method for producing a 3-butadiene / 1-butene 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 M represents an integer of 1 to 5, and n represents an integer of 1 to 5.), wherein the 1,3-butadiene · according to any one of claims 1 to 3 is represented. A method for producing a 1-butene copolymer. The transition metal complex catalyst is represented by 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. 5 is an alkyl group, and X represents a chlorine atom or a bromine atom.) The 1,3-butadiene / 1-butene copolymer according to any one of claims 1 to 4, A method for producing a polymer.   6. The 1,3-butadiene / 1-butene copolymer according to claim 1, wherein the transition metal complex catalyst is vanadyl-di- (2,2-dimethylpropoxy) -chloride. Manufacturing method of coalescence. 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 1,3-butadiene / 1-butene copolymer according to any one of claims 1 to 6, wherein a hydrocarbon group having 1 to 10 carbon atoms) or aluminoxane is used.   The method for producing a 1,3-butadiene / 1-butene copolymer according to claim 7, wherein the promoter is triisobutylaluminum. Before Symbol mixed-solution of 1,3-butadiene according to claim 1, wherein the butene to the 1,3-butadiene are characterized by being present in an amount of 1~300mol% · A method for producing a 1-butene copolymer. Butene before Symbol mixed-solution comprises a 1-butene, and cis-2-butene, claim characterized in that it contains trans-2-butene, at least one selected from the group consisting of isobutene 1 10. A method for producing a 1,3-butadiene / 1-butene copolymer according to any one of 9 above. Before Symbol mixed-solution method of producing a 1,3-butadiene-1-butene copolymer according to claim 1, characterized in that the C4 fraction.   The 1,3-butadiene / 1-butene copolymer has a content of structural units derived from 1-butene of 20 to 80 mol%. A method for producing a 3-butadiene / 1-butene copolymer.

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