JP5557710B2 - Copolymer - Google Patents

Description

The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound, and particularly relates to a copolymer having no portion in which monomer units of the non-conjugated olefin are continuously arranged. Is.

  When two or more types of monomers are polymerized in the same reaction system, a copolymer containing these monomer units as a repeating unit in one polymer chain is produced. Random copolymers, alternating copolymers, block copolymers, graft copolymers and the like are classified according to the arrangement of the body units. However, the arrangement of monomer units in the polymerization reaction between a conjugated diene compound and a non-conjugated olefin has not been reported.

For example, Japanese Unexamined Patent Publication No. 2000-154210 (Cited Document 1) discloses a conjugated diene polymerization catalyst containing a Group IV transition metal compound having a cyclopentadiene ring structure. Examples of the polymerizable monomer include α-olefins such as ethylene, but there is no mention of the arrangement of monomer units in the copolymer. Japanese Patent Laid-Open No. 2006-249442 (Cited Document 2) discloses a copolymer of an α-olefin and a conjugated diene compound, but the arrangement of monomer units in the copolymer is completely different. Not mentioned. Also, JP-T-2006-503141 (Cited document 3) discloses a copolymer of ethylene and butadiene synthesized using a special organometallic complex as a catalyst component, but butadiene as a monomer. Is only inserted into the copolymer in the form of trans-1,2-cyclohexane, and no mention is made of the arrangement of the monomer units in the copolymer.

JP 2000-154210 A JP 2006-249442 A JP-T-2006-503141

  Accordingly, an object of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound, wherein there is no portion where the monomer units of the non-conjugated olefin are continuously arranged. It is to provide a polymer.

  As a result of intensive studies to achieve the above object, the present inventors have polymerized a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound in the presence of a specific catalyst, thereby producing a single unit of the non-conjugated olefin. It has been found that a copolymer having no portion in which monomer units are continuously arranged can be obtained, and the present invention has been completed.

That is, the copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin outside the conjugated diene compound, and a portion in which the monomer units of the non-conjugated olefin are continuously arranged. Do rather, is a cis-1,4 bond content of the conjugated diene compound portion of 30% or more, 1,2-vinyl bond content of the conjugated diene compound portion is not more than 5%, the copolymer is praseodymium compound or It is obtained by polymerizing a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound in the presence of a reaction product of a praseodymium compound and a Lewis base .

In the copolymer of the present invention, the ratio (A / B) of the content (A) (mol%) of the non-conjugated olefin and the content (B) (mol%) of the conjugated diene compound is 0.1 / 99.9. It is preferably in the range of ~ 20/80.

  In a preferred example of the copolymer of the present invention, the non-conjugated olefin is an acyclic olefin.

In another preferred embodiment of the copolymer of the present invention, the non-conjugated olefin is an α-olefin.

In another preferred embodiment of the copolymer of the present invention, the non-conjugated olefin has 2 to 10 carbon atoms. Here, as said nonconjugated olefin, ethylene, propylene, and 1-butene are preferable.

  In another preferred embodiment of the copolymer of the present invention, the conjugated diene compound has 4 to 8 carbon atoms. Here, as the conjugated diene compound, 1,3-butadiene and isoprene are preferable.

  Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex.

  According to the present invention, a copolymer of a conjugated diene compound and a nonconjugated olefin other than the conjugated diene compound, wherein the copolymer has no portion in which the monomer units of the nonconjugated olefin are continuously arranged. Can be provided.

6 is a ¹³ C-NMR spectrum chart of copolymer B. 3 is a ¹³ C-NMR spectrum chart of copolymer C. FIG. 3 is a ¹³ C-NMR spectrum chart of copolymer F. FIG.

The present invention is described in detail below. The copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound, and monomer units of the non-conjugated olefin other than the conjugated diene compound are continuously arranged. The feature is that there is no part. In the present invention, a copolymer having no portion in which monomer units of non-conjugated olefins other than the conjugated diene compound are continuously arranged is referred to as a completely random copolymer. Further, nuclear magnetic resonance (NMR) is used as a main measuring means for confirming the formation of a completely random copolymer. Specifically, when a peak derived from a chain structure of a non-conjugated olefin other than a conjugated diene compound (for example, a peak appearing in the vicinity of 29.4 to 29.7 ppm in the case of ethylene) is not observed, the copolymer contains a conjugated diene. It shows that the monomer units of non-conjugated olefins other than the compound are not continuously arranged.

The copolymer of the present invention is a completely random copolymer and has no crystallization temperature (Tm) derived from homopolymerization of non-conjugated olefins other than the conjugated diene compound. Heat resistance at around 100-120 ° C is improved. In addition, the copolymer of the present invention is irregular in the arrangement of the monomer units of the conjugated diene compound, that is, may contain a portion in which the monomer units of the conjugated diene compound are continuously arranged. It is different from coalescence. In the case of the alternating copolymer, Tm is observed at around 50 ° C., and there is a possibility that the heat resistance at around 50 ° C. may be lowered. However, in the copolymer of the present invention, a non-conjugated olefin other than the conjugated diene compound is used. Since there is no crystallization temperature (Tm) derived from the homopolymerization, no such problem occurs.
In addition, "it is a complete random copolymer" shows that the monomer unit of nonconjugated olefins other than a conjugated diene compound is not arranging continuously.

In the copolymer of the present invention, the cis-1,4 bond amount of the conjugated diene compound portion is preferably 30% or more, and the 1,2-vinyl bond amount of the conjugated diene compound portion is preferably 5% or less. If the cis-1,4 bond content of the conjugated diene compound part is 30% or more and the 1,2-vinyl bond content is 5% or less, high elongation crystallinity and low glass transition point (Tg) can be maintained. Thus, physical properties such as wear resistance are improved.

In the copolymer of the present invention, the ratio (A / B) of the content (A) (mol%) of the non-conjugated olefin and the content (B) (mol%) of the conjugated diene compound is 0.1 / 99.9. It is preferably in the range of ~ 20/80. When the content of the non-conjugated olefin other than the conjugated diene compound is 0.1 to 20 mol%, the heat resistance can be effectively improved without causing phase separation. Moreover, if content of a conjugated diene compound is 99.9-80 mol%, the copolymer of this invention can behave uniformly as an elastomer.

The copolymer of the present invention does not have a problem of lowering the molecular weight, and its weight average molecular weight (Mw) is not particularly limited. However, from the viewpoint of application to a polymer structural material, the copolymer The polystyrene-converted weight average molecular weight (Mw) of the coalescence is preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 5 or less. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The conjugated diene compound used as the monomer preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

On the other hand, non-conjugated olefins other than the conjugated diene compound used as a monomer have excellent heat resistance and the ratio of double bonds in the main chain of the copolymer to reduce crystallinity. It is possible to increase the degree of design freedom. The non-conjugated olefin is preferably an acyclic olefin, and more preferably an α-olefin. Furthermore, it is preferable that carbon number of this nonconjugated olefin is 2-10. Accordingly, non-conjugated olefins other than the conjugated diene compound include ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 1-heptene, 1-octene and the like are preferable. Among these, ethylene, propylene and 1-butene are preferable. Non-conjugated olefins other than these conjugated diene compounds may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  Next, the manufacturing method of the copolymer of this invention is demonstrated in detail. The method for producing a copolymer of the present invention includes a step of polymerizing a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound in the presence of a praseodymium compound or a reaction product of a praseodymium compound and a Lewis base. Features. As a result of studying a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base with respect to the catalyst system used for coordination anion polymerization, the present inventors have selected a random random copolymer by selecting praseodymium as the rare earth element. It was found that a coalescence could be synthesized.

  According to the method for producing a copolymer of the present invention, there is no particular limitation except that a praseodymium compound or a reaction product of a praseodymium compound and a Lewis base is used as a catalyst, and a method for producing a polymer using a normal coordination ion polymerization catalyst. In the same manner, a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound can be copolymerized. As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, hexane, a cyclohexane, etc. are mentioned.

The praseodymium compound is preferably a praseodymium compound containing one or more kinds of ligands selected from a hydrogen atom, a halogen atom and an organic compound residue, preferably praseodymium is a trivalent salt or complex compound. More preferably it is. Further, the praseodymium compound or a reaction product of the praseodymium compound and a Lewis base includes a metallocene complex represented by the general formula (I) and the general formula (II), and a half metallocene represented by the general formula (III). It can be selected from the group consisting of a cationic complex and a praseodymium compound represented by the above general formula (IV) or a reaction product of a praseodymium compound and a Lewis base.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. In addition, two Cp ^R in the general formula (I) and the formula (II) may be the same or different from each other.

In the half metallocene cation complex represented by the general formula (III), Cp ^R ′ in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^R 'having a cyclopentadienyl ring as a basic skeleton include the following.

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^R ′ having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^R ′ having the fluorenyl ring as a basic skeleton is C ₁₃ H _9-X R _X
Or it may be represented by C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. The alkyl group is preferably a methyl group.

The metallocene complex represented by the general formula (II) contains a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group; phenoxy group and 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, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thio sec-butoxy group, a thio tert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-
Butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group And arylthiolate groups such as 2-isopropyl-6-thioneopentylphenoxy group and 2,4,6-triisopropylthiophenoxy group, among which 2,4,6-triisopropylthiophenoxy group is preferable.

In the general formula (III), the amide group represented by X includes aliphatic amide groups such as dimethylamide group, diethylamide group and diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

In the general formula (III), the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

In the general formula (III), X is a bistrimethylsilylamide group or a carbon number of 1-2.
Zero hydrocarbon groups are preferred.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate is exemplified, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

The metallocene complex represented by the general formula (I) includes, for example, praseodymium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and a bis (trialkylsilyl) amide salt (for example, potassium salt or It can be obtained by reacting with a lithium salt. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (I) are shown below.

(In the formula, X ′ ″ represents a halide.)

In the metallocene complex represented by the general formula (II), for example, praseodymium trishalide is reacted with an indenyl salt (for example, potassium salt or lithium salt) and a silyl salt (for example, potassium salt or lithium salt) in a solvent. Can be obtained. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (II) are shown below.

(In the formula, X ′ ″ represents a halide.)

The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (V), Cp ^R ′ each independently represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom or an alkoxide group. , A thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Nitrotetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In addition, the general formula [A] ⁺ [
B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, the metallocene complex represented by the general formula (I) or the formula (II) and the general formula [A] ⁺ [B]
^- by using a combination of an ionic compound represented by, it is also possible to form the half metallocene cation complex represented by the general formula (III) in the reaction system.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are preferably determined by X-ray structural analysis.

In the praseodymium compound represented by the general formula (IV) or a reaction product of the praseodymium compound and a Lewis base, as a group (ligand) bonded to praseodymium of the praseodymium compound, specifically, a hydrogen atom; a methoxy group, Aliphatic alkoxy groups such as ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropyl Phenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group;
Aliphatic thiolate groups such as thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio sec-butoxy group, thio tert-butoxy group; thiophenoxy group, 2,6-di-tert -Butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentyl group Arylthiolate groups such as phenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group; aliphatic amide groups such as dimethylamide group, diethylamide group, diisopropylamide group; phenyl Amide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dyneopen Ruphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6- arylamide groups such as tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group; trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropyl Silyl groups such as silyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl, tert-butyl, neopentyl, hexyl, oct Linear or branched aliphatic hydrocarbon groups such as ruthel groups; aromatic hydrocarbon groups such as phenyl, tolyl and naphthyl groups; aralkyl groups such as benzyl groups; cyclopentadienyl, indenyl, fluorenyl, etc. A cyclic hydrocarbon group; a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group or a bistrimethylsilylmethyl group; Furthermore, aldehyde residues such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone 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, bivaric acid, versatic acid [from Shell Chemical Co., Ltd., a mixture of isomers of C10 monocarboxylic acid Composed Residues of carboxylic acids such as synthetic acid], phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid and succinic acid; thiocarboxylic acids such as hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid and thiobenzoic acid Residues of dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), Dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid Residues of phosphate esters such as (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl); 2-ethylhexylphosphonate monobutyl, 2- Ethyl hex Ruhosuhon acid mono -
2-ethylhexyl, mono-2-ethylhexyl phenylphosphonate, 2-ethylhexylphosphonate mono-p-nonylphenyl, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate Phosphonic acid ester residues such as phosphonic acid mono-p-nonylphenyl, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, geo Reylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethyl) (Hexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, olei Phosphinic acid, lauric acid phosphine,
Mention may also be made of phosphinic acid residues such as phenylphosphinic acid and p-nonylphenylphosphinic acid. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

  Further, in the praseodymium compound represented by the general formula (IV) or a reaction product of the praseodymium compound and a Lewis base, examples of the Lewis base that reacts with the praseodymium compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, Examples thereof include lithium chloride, neutral olefins, and neutral diolefins. Here, when the praseodymium compound reacts with a plurality of Lewis bases (in the formula (IV), when w is 2 or 3), the Lewis bases L ′ may be the same or different.

In the method for producing a copolymer of the present invention, the praseodymium compound or a reaction product of a praseodymium compound and a Lewis base (hereinafter also referred to as component (A)) is an ion comprising a non-coordinating anion and a cation. Compound (B-1), aluminoxane (B-2), and a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and at least one halogen compound (B-3). At least one selected from the group (
You may use the catalyst system combined with B) component. In addition, it is preferable that the total usage-amount of (B) component is 0.1-50 times mole with respect to (A) component.

The ionic compound represented by (B-1) comprises a non-coordinating anion and a cation, and reacts with a reaction product of the praseodymium compound or its Lewis base as the component (A) to form a cationic transition. Examples thereof include ionic compounds capable of generating metal compounds. Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate,
Tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundeborate . On the other hand, as a cation,
Examples thereof include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation, and more specifically, as a tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium such as diisopropylammonium cation and dicyclohexylammonium cation And cations. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Therefore, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Nitrotetrakis (pentafluorophenyl) borate and the like are preferable. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, it is preferable that the usage-amount of the said ionic compound is 0.1-10 times mole with respect to (A) component, and it is still more preferable that it is about 1 times mole.

The aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, the repetition represented by the general formula: (—Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used. The amount of the aluminoxane used is preferably such that the element ratio Al / Pr of praseodymium Pr constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000.

  The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). It can react with a reaction product with a praseodymium compound or a Lewis base thereof to produce a halogenated transition metal compound or a compound having a transition metal center with insufficient charge. In addition, it is preferable that the total usage-amount of the said halogen compound is 1-5 times mole with respect to (A) component.

As the Lewis acid, a boron-containing halogen compound such as B (C ₆ F ₅ ) _{3 and} an aluminum-containing halogen compound such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable.

  The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, Benzoylacetone, propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid , Oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol, oleyl Alcohol, stearyl alcohol, phenol,
Benzyl alcohol, 1-decanol, lauryl alcohol, etc. Among them, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of the organic compound containing the active halogen include benzyl chloride.

In addition, when the component (B) is at least one of the ionic compound (B-1) and the halogen compound (B-3), the component (A) and the component (B)
Component (C): the following general formula (VI):
YR ¹ _a R ² _b R ³ _c ... (VI)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. A hydrocarbon group or a hydrogen atom, R ³
Is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a metal selected from Group 1 of the Periodic Table. In some cases, a is 1 and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0. And when Y is a metal selected from Group 13 of the Periodic Table, a, b, and c are 1]. Since the ionic compound (B-1) and the halogen compound (B-3) have no carbon atom to supply to the component (A), the component (C) is used as a carbon source to the component (A). Is required. In addition, even if (B) component is aluminoxane (B-2), (C) component can be combined with (A) component and (B) component. In addition, the component (A) may contain other components contained in a normal rare earth element compound catalyst system, such as a promoter.

The component (C) is represented by the following general formula (VII):
AlR ¹ R ² R ³ ... (VII)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound of the formula (VII) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, hydrogenated Diisohexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum dihydride, Examples thereof include sobutylaluminum dihydride, and among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. The organometallic compound as component (C) described above can be used singly or in combination of two or more. In addition, it is preferable that the usage-amount of the said organometallic compound is 1-50 times mole with respect to (A) component.

  As described above, the method for producing a copolymer of the present invention produces a polymer by a polymerization reaction using a conventional coordination ion polymerization catalyst, except that the catalyst system comprising the above-described component (A) is used as a polymerization catalyst. It can be similar to the method. Here, the method for producing a copolymer of the present invention includes, for example, (1) a component of a catalyst system in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. It may be provided separately and used as a catalyst system in the reaction system, or (2) a catalyst system prepared in advance may be provided in the polymerization reaction system. In addition, the usage-amount of (A) component has the preferable range of 0.0001-0.01 times mole with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.

In the method for producing a copolymer of the present invention, the polymerization reaction of a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of -100 ° C to 200 ° C, for example, and can be about room temperature. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. The pressure for the polymerization reaction is preferably in the range of 0.1 to 5.0 MPa in order to sufficiently incorporate the conjugated diene compound and the non-conjugated olefin other than the conjugated diene compound into the polymerization reaction system. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of, for example, 1 second to 10 days, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. it can.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of Pr {N (SiMe ₃ ) ₂ } ₃ >
Under a nitrogen atmosphere, 30 mL of an ether solution containing KN (SiMe ₃ ) ₂ (2.40 g, 12.03 mmol) (Aldrich) is slowly added dropwise to 100 mL of a THF solution of PrCl ₃ (0.989 g, 4.00 mmol) (Strem). And stirred at room temperature for 12 hours. Thereafter, the solvent was distilled off under reduced pressure, 200 mL of hexane was added instead, and the precipitate was filtered. Thereafter, hexane was slowly distilled off under reduced pressure to obtain Pr {N (SiMe ₃ ) ₂ } ₃ (2.73 g, yield 68%) as yellow crystals.

<Synthesis of _{(C 5 H 5) Pr {} N (SiMe 3) 2} 2 (thf)>
Under a nitrogen atmosphere, 100 mL of a THF solution of PrCl ₃ (1.53 g, 6.19 mmol) (manufactured by Strem Co.)
3.2 mL of a THF solution (manufactured by Aldrich) containing Na (C ₅ H ₅ ) (6.40 mmol) was slowly added dropwise and stirred at room temperature for 90 minutes. Thereafter, 30 mL of an ether solution containing KN (SiMe ₃ ) ₂ (2.40 g, 12.03 mmol) (manufactured by Aldrich) was slowly added dropwise and stirred at room temperature for 12 hours. Thereafter, the solvent was distilled off under reduced pressure, 200 mL of hexane was added instead, and the precipitate was filtered. after that,
When hexane was slowly distilled off under reduced pressure, green crystals of (C ₅ H ₅ ) Pr {N (SiMe ₃ ) ₂ } ₂ (thf) (0.38 g, yield 11%) were obtained.

<Synthesis of (2-MeC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ }>
Under a nitrogen atmosphere, Pr {N (SiMe ₃ ) ₂ } ₃ (0.38 g, 0.61 mmol), 2-MeC ₉ H ₇ (0.16 g, 1.23 mmol) (manufactured by Aldrich), and HN (SiHMe ₂ ) ₂ (0.27 g, 2.00 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred and reacted in 10 mL of hexane at room temperature for 1 hour. The reaction solution was filtered, and the residue was washed several times with hexane, and then hexane was slowly distilled off under reduced pressure to give (2-MeC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) _{2 as} a yellow powder. } (0.22 g, 68%) was obtained.

<Synthesis of (2-PhC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ }>
Under a nitrogen atmosphere, Pr {N (SiMe ₃ ) ₂ } ₃ (0.62 g, 1.00 mmol), 2-PhC ₉ H ₇ (0.38 g, 1.98 mmol) (manufactured by Aldrich), and HN (SiHMe ₂ ) ₂ (0.40 g, 3.00 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred and reacted in 50 mL of hexane at 65 ° C. for 1 hour. After returning to room temperature, the reaction solution was filtered and the residue was washed several times with hexane. Thereafter, hexane was slowly distilled off under reduced pressure to obtain (2-PhC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ } (0.41 g, 62%) as a yellow powder.

<Synthesis of (2-Ph-1-MeC ₉ H ₅ ) ₂ Pr {N (SiHMe ₂ ) ₂ }>
Under a nitrogen atmosphere, Pr {N (SiMe ₃ ) ₂ } ₃ (0.38 g, 0.61 mmol), 2-PhC ₉ H ₇ and BuLi
2-Ph-1-MeC ₉ H ₆ (0.24 g, 1.16 mmol) and HN (SiHMe ₂ ) ₂ (0.27 g, 2.02 mmol) (Tokyo Kasei Co., Ltd.) obtained from the reaction of MeLi (manufactured by Aldrich) Product) hexane 10mL
The mixture was stirred for 72 hours at room temperature. The reaction solution was filtered, and the residue was washed several times with toluene. After that, the solvent was slowly concentrated under reduced pressure, and allowed to stand at −30 ° C. overnight to form yellowish green crystals (2-Ph-1- MeC ₉ H ₅ ) ₂ Pr {N (SiHMe ₂ ) ₂ } (0.18 g, 45%) was obtained.

Example 1
After adding 120 ml of a toluene solution containing 2.83 g (0.052 mol) of 1,3-butadiene to a sufficiently dry 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, trisbistrimethylsilylamide praseodymium Pr {N (SiMe ₃ ) ₂ } ₃ 27.0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 27.0 μmol and 1.35 mmol of triisobutylaluminum were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at 80 ° C. for 60 minutes. After polymerization, 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 mass%
The reaction was stopped by adding 1 ml of an isopropanol solution, and the copolymer was separated with a large amount of methanol, followed by vacuum drying at 70 ° C. to obtain a polymer A. The yield of the obtained copolymer A was 1.82 g.

(Example 2)
Instead of Pr {N (SiMe ₃ ) ₂ } ₃ , (cyclopentadienyl) praseodymium bis (bistrimethylsilylamide) (tetrahydrofuran) (C ₅ H ₅ ) Pr {N (SiMe ₃ ) ₂ } ₂ (thf)
When the experiment was conducted in the same manner as in Example 1 except that the polymerization time was changed to 30 minutes, copolymer B was obtained in a yield of 2.40 g.

(Example 3)
Instead of Pr {N (SiMe ₃ ) ₂ } ₃ , bis (2-methylindenyl) praseodymium bis (dimethylsilylamide) (2-MeC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ } is used, Furthermore, an experiment was conducted in the same manner as in Example 1 except that the polymerization time was changed to 60 minutes. As a result, copolymer C was obtained in a yield of 2.00 g.

(Example 4)
Instead of Pr {N (SiMe ₃ ) ₂ } ₃ , bis (2-phenylindenyl) praseodymium bis (
Dimethylsilylamide) (2-PhC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ } was used, and the experiment was conducted in the same manner as in Example 1 except that the polymerization time was changed to 135 minutes. Copolymer D was obtained in a yield of 2.20 g.

(Example 5)
Instead of Pr {N (SiMe ₃ ) ₂ } ₃ , bis (2-phenyl-1-methylindenyl) praseodymium bis (dimethylsilylamide) (2-Ph-1-MeC ₉ H ₅ ) ₂ Pr {N ( An experiment was conducted in the same manner as in Example 1 except that SiHMe ₂ ) ₂ } was used and the polymerization time was changed to 30 minutes. As a result, copolymer E was obtained in a yield of 2.68 g.

(Comparative Example 1)
After adding 320 ml of a toluene solution containing 3.95 g (0.073 mol) of 1,3-butadiene to a sufficiently dry 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.6 MPa. On the other hand, dimethylaluminum (μ-dimethyl) bis (2-phenylindenyl) neodium [(2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe _{2 is} placed in a glass container in a glove box under a nitrogen atmosphere. ] 204.0 μmol and triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃
CB (C ₆ F ₅ ) ₄ ) 195.0 μmol was charged and dissolved in 20 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at room temperature for 90 minutes. After polymerization, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (N
S-5) 1 ml of 5% by mass isopropanol solution was added to stop the reaction, and the copolymer was further separated with a large amount of methanol, followed by vacuum drying at 70 ° C. to obtain copolymer F. The yield of the obtained copolymer F was 3.60 g.

  For the copolymers A to E of Examples 1 to 5 and the copolymer F of Comparative Example 1 produced as described above, the microstructure, ethylene content, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) was measured and evaluated by the following method.

(1) Microstructure The microstructure of the butadiene moiety in the copolymer was measured with ¹ H-NMR spectrum (amount of 1,2-vinyl bond) and ¹³ C-NMR spectrum (cis-1,4 bond and trans-1). , 4-bond content ratio). The calculated values of cis-1,4 bond amount (%) and 1,2-vinyl bond amount (%) are shown in Table 1.
(2) Content of ethylene The content (mol%) of the ethylene moiety in the copolymer was determined from the integral ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum.
(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Monodispersed polystyrene was analyzed by gel permeation chromatography [GPC: HLC-8121GPC / HT manufactured by Tosoh Corporation, column: GMH _HR- H (S) HT (two in series) manufactured by Tosoh Corporation, detector: differential refractometer (RI)]. As a reference, the polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined.

FIG. 1 shows a ¹³ C-NMR spectrum chart of copolymer B, and FIG.
It shows the ¹³ C-NMR spectrum chart, Figure 3 shows a ¹³ C-NMR spectrum chart of a copolymer F. ¹³ C-NMR was measured at 100 ° C. using tetrachloroethane as a solvent. In FIGS. 1 and 2, since the peak derived from the chain structure of ethylene cannot be observed at 29.4 to 29.7 ppm, the copolymer B of Example 2 and the copolymer C of Example 3 are non-conjugated other than the conjugated diene compound. It can be seen that the copolymer has no portion in which the olefin monomer units are continuously arranged, that is, a completely random copolymer. On the other hand, in FIG. 3, a peak derived from the chain structure of ethylene is observed at 29.4 to 29.7 ppm. In addition, similarly to the copolymer B of Example 2 and the copolymer C of Example 3, the peaks derived from the chain structure of ethylene for the copolymers A, D and E of Examples 1, 4 and 5 are Not observed.

  The copolymer of the present invention can be used for elastomer products in general, particularly for tire members.

Claims (8)

And a conjugated diene compound, a copolymer of a non-conjugated olefin outside conjugated diene compound, said parts monomer units are successively arranged nonconjugated olefins rather name
The amount of cis-1,4 bonds in the conjugated diene compound portion is 30% or more, and the amount of 1,2-vinyl bonds in the conjugated diene compound portion is 5% or less,
The copolymer is obtained by polymerizing a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound in the presence of a praseodymium compound or a reaction product of a praseodymium compound and a Lewis base. Coalescence.   The ratio (A / B) between the content (A) (mol%) of the non-conjugated olefin and the content (B) (mol%) of the conjugated diene compound is 0.1 / 99.9 to 20/80. The copolymer according to claim 1, wherein the copolymer falls within the range.   The copolymer according to claim 1, wherein the non-conjugated olefin is an acyclic olefin. The copolymer according to claim 1 or 3 , wherein the non-conjugated olefin is an α-olefin. 5. The copolymer according to claim 1, 3 or 4 , wherein the non-conjugated olefin has 2 to 10 carbon atoms. 6. The copolymer according to claim 5 , wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene and 1-butene.   The copolymer according to claim 1, wherein the conjugated diene compound has 4 to 8 carbon atoms. The copolymer according to claim 7 , wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.