JP5612512B2 - Rubber composition, crosslinked rubber composition, and tire - Google Patents

Description

  The present invention relates to a rubber composition, a crosslinked rubber composition, and a tire, and is particularly used for producing a rubber excellent in roll processability and bending fatigue resistance, and is a block copolymer of a conjugated diene compound and a nonconjugated olefin. Rubber composition comprising polymer and random copolymer in which monomer units of conjugated diene compound and non-conjugated olefin are irregularly arranged, and crosslinked rubber composition obtained by crosslinking the rubber composition And a tire using the rubber composition or the crosslinked rubber composition.

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, there has been almost no report on the arrangement of monomer units in the polymerization reaction between a conjugated diene compound and a non-conjugated olefin, and there has been no report on a mixture of a block copolymer and a random copolymer. It has not been.

For example, Japanese Patent Laid-Open No. 2000-154210 (Patent Document 1) discloses a conjugated diene polymerization catalyst containing a Group IV transition metal compound having a cyclopentadiene ring structure, which is co-polymerized with the conjugated diene. 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 (Patent 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. Further, JP-T-2006-503141 (Patent Document 3) discloses a copolymer of ethylene and butadiene synthesized using a special organometallic complex as a catalyst component. Is inserted into the copolymer in the form of trans-1,2-cyclohexane, and the arrangement of the monomer units in the copolymer is not mentioned at all. There is no description or suggestion that a rubber excellent in roll processability and bending fatigue resistance can be obtained by mixing a polymer and a random copolymer.

  Further, JP-A-11-228743 (Patent Document 4) discloses an unsaturated elastomer composition comprising an unsaturated olefin copolymer and rubber, but the monomer in the copolymer. The unit arrangement is merely described as being random, and a mixture obtained by mixing a block copolymer and a random copolymer is not disclosed. In addition, there is no description or suggestion that a rubber excellent in roll processability and bending fatigue resistance can be obtained by mixing a block copolymer and a random copolymer.

JP 2000-154210 A JP 2006-249442 A JP-T-2006-503141 JP-A-11-228743

  Therefore, an object of the present invention is to produce a rubber having excellent roll processability and bending fatigue resistance, and a block copolymer of a conjugated diene compound and a nonconjugated olefin, and a conjugated diene compound and a nonconjugated olefin. A rubber composition comprising a random copolymer in which the monomer units are irregularly arranged, a crosslinked rubber composition obtained by crosslinking the rubber composition, and the rubber composition or the crosslinked rubber The object is to provide a tire using the composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a block copolymer of a conjugated diene compound and a nonconjugated olefin, and monomer units of the conjugated diene compound and the nonconjugated olefin are irregularly arranged. By using a rubber composition containing a random copolymer formed as described above, it has been found that a rubber excellent in roll processability and bending fatigue resistance can be obtained, and the present invention has been completed.

  That is, the rubber composition of the present invention includes a block copolymer of a conjugated diene compound and a non-conjugated olefin, a random copolymer formed by irregularly arranging monomer units of the conjugated diene compound and the non-conjugated olefin, and , Including.

  The rubber composition of the present invention preferably has a mass ratio of 95/5 to 5/95 of the block copolymer and the random copolymer.

  In the rubber composition of the present invention, the block copolymer and the random copolymer preferably have a cis-1,4 bond content of the conjugated diene compound-derived portion of 50% or more.

  In the rubber composition of the present invention, the block copolymer and the random copolymer have a 1,2 adduct portion (including a 3,4 adduct portion) content of the conjugated diene compound in the conjugated diene compound-derived portion. It is preferable that it is 5% or less.

  In the rubber composition of the present invention, the content of the non-conjugated olefin-derived portion in the block copolymer is preferably more than 0 mol% and 50 mol% or less.

  In the rubber composition of the present invention, the block copolymer and the random copolymer preferably have a weight average molecular weight in terms of polystyrene of 10,000 to 10,000,000.

  In the rubber composition of the present invention, the molecular weight distribution (Mw / Mn) of the block copolymer and the random copolymer is preferably 10 or less.

  In the rubber composition of the present invention, the non-conjugated olefin is preferably an acyclic olefin.

  In the rubber composition of the present invention, the non-conjugated olefin preferably has 2 to 10 carbon atoms.

  In the rubber composition of the present invention, the non-conjugated olefin is preferably at least one selected from the group consisting of ethylene, propylene and 1-butene.

  In the rubber composition of the present invention, the non-conjugated olefin is preferably ethylene.

  In the rubber composition of the present invention, the conjugated diene compound is preferably at least one selected from the group consisting of 1,3-butadiene and isoprene.

  The rubber composition of the present invention preferably contains 5 to 200 parts by mass of a reinforcing filler and 0.1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the rubber component.

  The crosslinked rubber composition of the present invention is obtained by crosslinking the rubber composition of the present invention.

  The tire of the present invention is characterized by using the rubber composition of the present invention or the crosslinked rubber composition of the present invention.

  According to the present invention, a block copolymer of a conjugated diene compound and a non-conjugated olefin, and a conjugated diene compound and a non-conjugated olefin are used to produce a rubber excellent in roll processability and bending fatigue resistance. A rubber composition comprising a random copolymer in which monomer units are irregularly arranged, a crosslinked rubber composition obtained by crosslinking the rubber composition, and the rubber composition or the crosslinked rubber composition A tire using can be provided.

The DSC curve of the block copolymer A is shown. The DSC curve of the random copolymer B is shown. The ¹³ C-NMR spectrum chart of the block copolymer A is shown. The ¹³ C-NMR spectrum chart of random copolymer B is shown.

(Rubber composition)
The present invention is described in detail below. The rubber composition of the present invention comprises at least a block copolymer and a random copolymer, and if necessary, a rubber component other than the block copolymer and the random copolymer, and a reinforcing filling Agent, crosslinking agent, and other components.

<Block copolymer and random copolymer>
-Block copolymer-
The block copolymer is not particularly limited as long as it is a block copolymer of a conjugated diene compound and a non-conjugated olefin, and can be appropriately selected according to the purpose.
The block copolymer has a block portion composed of a monomer unit of a non-conjugated olefin and exhibits static crystallinity, so that it is excellent in mechanical properties such as breaking strength. Moreover, since the said block copolymer is provided with the block part which consists of a monomer unit of a conjugated diene compound, it becomes possible to act as an elastomer.

  Here, with respect to the block copolymer, differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) are used as main measurement means for confirming the formation of the block copolymer. The differential scanning calorimetry (DSC) is a measurement method performed in accordance with JIS K 7121-1987. Specifically, by DSC, a glass transition temperature derived from a block portion composed of monomer units of a conjugated diene compound, a crystallization temperature derived from the block portion, and a block portion composed of monomer units of a non-conjugated olefin. If the crystallization temperature can be observed, it is confirmed that a block part consisting of monomer units of the conjugated diene compound and a block part consisting of monomer units of the non-conjugated olefin are formed in the copolymer. Show.

The block copolymer preferably has a cis-1,4 bond content of the conjugated diene compound-derived moiety of 50% or more, more preferably 75% or more. If the cis-1,4 bond content of the conjugated diene compound-derived portion is 50% or more, the block portion consisting of the monomer unit of the conjugated diene compound exhibits high elongation crystallinity, and therefore, the breaking strength, fatigue resistance, etc. The mechanical properties can be further improved. In the composition ratio within the range of the present invention, the cis chain of the conjugated diene may be distributed continuously or discontinuously.
The amount of cis-1,4 bonds is the amount in the portion derived from the conjugated diene compound, and is not a ratio relative to the entire block copolymer.

  The block copolymer preferably has a non-conjugated olefin-derived content of more than 0 mol% and less than 100 mol%. When the content of the non-conjugated olefin-derived portion is within the above specified range, mechanical properties such as breaking strength can be improved more reliably. Further, from the viewpoint of improving mechanical properties such as breaking strength without causing phase separation of the copolymer, the content of the non-conjugated olefin-derived portion is more preferably more than 0 mol% and not more than 50 mol%. .

  On the other hand, in the block copolymer, the content of the conjugated diene compound-derived moiety is preferably more than 0 mol% and less than 100 mol%, more preferably 50 mol% or more and less than 100 mol%. If the content of the conjugated diene compound-derived moiety is within the above specified range, the block copolymer can behave uniformly as an elastomer.

Examples of the structure of the block copolymer include (AB) _x , A- (BA) _x , B- (AB) _{x, and the} like. Here, A is a block part composed of monomer units of non-conjugated olefin, B is a block part composed of monomer units of conjugated diene compound, and x is an integer of 1 or more, preferably It is an integer of 1-5. Note that the boundaries between the block portions do not need to be clearly distinguished, for example, a portion made of a mixture of a conjugated diene compound and a non-conjugated olefin between the block portion A and the block portion B, a so-called tapered structure. May be formed. In addition, when a plurality of the same block portions are present in the copolymer, it is not necessary to arrange the types and compositions of the monomers constituting the block portions.

Further, the block copolymer has a 1,2-adduct (including a 3,4-adduct) content of the conjugated diene compound (including a 1,2-adduct portion of the conjugated diene compound (3,4) in the conjugated diene compound-derived portion). The content) (including the adduct portion) is preferably 5% or less. When the content of 1,2 adducts (including 3,4 adducts) in the conjugated diene compound portion is 5% or less, the rubber composition of the present invention containing the block copolymer has ozone resistance and fatigue resistance. The property can be further improved. Further, when the content of 1,2-adduct (including 3,4-adduct) of the conjugated diene compound portion is 2.5% or less, the rubber composition of the present invention containing the block copolymer has a resistance to resistance. Ozone property and fatigue resistance can be further improved. The content of 1,2-adduct (including 3,4-adduct) in the conjugated diene compound portion is more preferably 2.0% or less.
The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound portion (including the 3,4-adduct portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.

-Random copolymer-
The random copolymer is a random copolymer of a conjugated diene compound and a non-conjugated olefin, in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged. When the differential scanning calorimetry of the copolymer is performed, the crystallization temperature derived from the block portion composed of monomer units of non-conjugated olefin is not observed. That is, the copolymer of the present invention has no block portion composed of monomer units of non-conjugated olefin, and the sequence of monomer units of non-conjugated olefin is a completely irregular sequence. It has a random part (also referred to as a random structure) in which monomer units of non-conjugated olefins are irregularly arranged. Thus, if the arrangement of the monomer units of the nonconjugated olefin is a completely irregular arrangement, a copolymer of a nonconjugated olefin having properties such as heat resistance can be obtained without causing phase separation of the copolymer. Can be introduced into the main chain. The differential scanning calorimetry (DSC) is a measurement method performed in accordance with JIS K 7121-1987. In addition, the copolymer of the present invention is referred to as a copolymer having no crystallinity because no crystallization temperature derived from a block portion composed of monomer units of non-conjugated olefin is observed in differential scanning calorimetry. You can also.

The random copolymer preferably has a cis-1,4 bond content of the conjugated diene compound-derived moiety of 50% or more, and more preferably 75% or more. More preferably, it is 75% or more, More preferably, it is 90% or more. If the cis-1,4 bond content of the conjugated diene compound-derived moiety is 50% or more, it is possible to retain the stretched crystallinity and the low glass transition point (Tg), thereby improving crack growth resistance and wear resistance. And other physical properties are improved. In the composition ratio within the range of the present invention, the cis chain of the conjugated diene may be distributed continuously or discontinuously.
The amount of cis-1,4 bonds is the amount in the portion derived from the conjugated diene compound, and is not a ratio relative to the entire random copolymer.

  In the random copolymer, the content of the non-conjugated olefin-derived portion is preferably more than 0 mol% and not more than 50 mol%, more preferably more than 0 mol% and not more than 20 mol%. If the content of the non-conjugated olefin-derived portion is within the above specified range, the heat resistance can be effectively improved without causing phase separation.

  On the other hand, the content of the conjugated diene compound-derived moiety in the random copolymer is preferably 50 mol% or more and less than 100 mol%, and more preferably 80 mol% or more and less than 100 mol%. If the content of the conjugated diene compound-derived portion is within the above specified range, the random copolymer can behave uniformly as an elastomer.

In addition, the random copolymer has a 1,2-adduct (including a 3,4-adduct) content of the conjugated diene compound (including a 1,2-adduct portion (3,4) of a conjugated diene compound in a portion derived from a conjugated diene compound). The content) (including the adduct portion) is preferably 5% or less. More preferably, it is 3% or less, More preferably, it is 2.5% or less.
When the content of 1,2-adduct (including 3,4-adduct) of the conjugated diene compound portion is 5% or less, the rubber composition of the present invention containing the random copolymer has ozone resistance and fatigue resistance. The property can be further improved. Further, when the content of 1,2-adduct (including 3,4-adduct) of the conjugated diene compound part is 2.5% or less, the rubber composition of the present invention containing the random copolymer has a resistance to resistance. Ozone property and fatigue resistance can be further improved.

  The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.

  The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound portion (including the 3,4-adduct portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.

-Mass ratio-
There is no restriction | limiting in particular as mass ratio of the said block copolymer and the said random copolymer, Although it can select suitably according to the objective, 95 / 5-5 / 95 are preferable, 80 / 20-10 / 90 is more preferable.
When the mass ratio is more than 95/5 or less, the characteristics of the present invention may be small or the characteristics may not be exhibited. When the mass ratio is less than 5/95, workability deteriorates. There is. On the other hand, when the mass ratio is within the more preferable range,
This is advantageous in terms of workability and bending fatigue resistance.

-Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)-
In the block copolymer and the random copolymer, the weight average molecular weight (Mw) is not particularly limited, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a molecular structure material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and 50 000 to 600,000 is more preferable. 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).

-Conjugated diene compounds-
In the block copolymer and the random copolymer, the conjugated diene compound used as a monomer preferably has 4 to 12 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.
Using any of the specific examples of the conjugated diene compound described above, the block copolymer and the random copolymer can be prepared by the same mechanism.

-Non-conjugated olefin-
On the other hand, in the block copolymer and the random copolymer, the non-conjugated olefin used as a monomer is a non-conjugated olefin other than the conjugated diene compound, and has excellent heat resistance and in the main chain of the copolymer. It is possible to increase the degree of freedom of design as an elastomer by reducing the proportion of double bonds occupied and reducing the crystallinity. Moreover, as a nonconjugated olefin, it is preferable that it is an acyclic olefin, and it is preferable that carbon number of this nonconjugated olefin is 2-10. Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred, with ethylene being particularly preferred. These non-conjugated olefins 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.

-Manufacturing method of block copolymer-
Next, the method for producing the block copolymer will be described in detail. However, the manufacturing method described in detail below is merely an example.
The first method for producing the block copolymer is characterized in that a conjugated diene compound and a non-conjugated olefin are polymerized in the presence of a polymerization catalyst composition shown below. 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, cyclohexane, mixtures thereof etc. are mentioned.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、そ
れぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^ａ〜Ｒ^ｆは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、そ
れぞれ独立して無置換もしくは置換インデニルを示し、Ｘ’は、水素原子、ハロゲン原子
、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基
を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセ
ン錯体、並びに下記一般式（ＩＩＩ）：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒ’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］⁻は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物（以下、第一重合触媒組成物ともいう）が挙げられ、該重合触媒組成物は、更に、通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分、例えば助触媒等を含んでいてもよい。ここで、メタロセン錯体は、一つ又は二つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり、特に、中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。なお、重合反応系において、第一重合触媒組成物に含まれる錯体の濃度は０．１〜０．０００１ｍｏｌ／ｌの範囲であることが好ましい。 <First polymerization catalyst composition>
The polymerization catalyst composition includes the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, 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), and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. 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. In the polymerization reaction system, the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

In the metallocene complexes represented by the general formula (I) and formula (II), Cp ^R in the formula is an unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton may 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 and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） In the half metallocene cation complex represented by the above 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 above 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 can be represented by C ₁₃ H _9-X R _X or 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 central metal M in the general formulas (I), (II) and (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{a to} R ^f in the general formula (I)) contained in the silylamide ligand 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 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) includes 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 a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy 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 thiosec-butoxy group, a thiotert-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-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.

  In the general formula (III), examples of the amide group represented by X include aliphatic amide groups such as a dimethylamide group, a diethylamide group, and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, 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 and 2,4,6-tri-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide Groups are preferred.

  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 any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an 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 preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

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 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, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the 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.

（式中、Ｘ’’はハライドを示す。） The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or 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. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

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

（式中、Ｘ’’はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or 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. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

(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 (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, 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 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

[A] Examples of the cation represented by ⁺ 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 a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by 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 for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. Further, the ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene complex. 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, by using a combination of a metallocene complex represented by the general formula (I) or the formula (II) and an ionic compound represented by the general formula [A] ⁺ [B] ⁻ A half metallocene cation complex represented by the formula (III) can also be formed.

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

The co-catalyst that can be used in the first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.

On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C _{1 to} C ₁₀ hydrocarbon group or a hydrogen atom, and R ″ is C ₁ an organoaluminum compound represented by a hydrocarbon group which the -C ₁₀₎ are preferred. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Furthermore, examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  Further, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

<Second polymerization catalyst composition>
In addition, as the polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can also be suitably mentioned. When the polymerization catalyst composition contains at least one of an ionic compound (B-1) and a halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (i):
YR ¹ _a R ² _b R ³ _c (i)
[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. R ³ is a hydrocarbon group or a hydrogen atom, and 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 periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and 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]. It is characterized by including. Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. Further, the polymerization catalyst composition may contain other components such as a co-catalyst contained in a normal rare earth element compound-based polymerization catalyst composition. In the polymerization reaction system, the concentration of the component (A) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

  The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed. The object does not have a bond between rare earth element and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII):
M ¹¹ X ¹¹ ₂ · L ¹¹ w (XI)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (XII)
[Wherein M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. Represents a group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3].

Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as 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, thio aliphatic thiolate groups such as sec-butoxy group and thio-tert-butoxy group; Noxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-tert-butyl Arylamide groups such as ru-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, iodine And halogen atoms such as atoms. Furthermore, residues of aldehydes 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 [trade name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as 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 (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Phosphonic acid ester residues such as mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A) used in the second polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L ¹¹ is the same or different. It may be.

  The component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of an ionic compound (B-1), an aluminoxane (B-2), and a halogen compound (B-3). is there. In addition, it is preferable that content of the sum total of (B) component in said 2nd polymerization catalyst composition is 0.1-50 times mole with respect to (A) component.

The ionic compound represented by the above (B-1) is composed of a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound or its Lewis base as the component (A) to be cationic. Examples thereof include ionic compounds capable of generating a transition metal compound. 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, tri Decahydride-7,8-dicarboundecaborate and the like can be mentioned. On the other hand, examples of the cation 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 trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as 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 (for example, 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 cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Accordingly, 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. Preferred is nitrotetrakis (pentafluorophenyl) borate. 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 it is 0.1-10 times mole with respect to (A) component, and, as for content of the ionic compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 1 time 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 aluminoxane content in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

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). Cationic transition metal compounds (halogenated transition metal compounds and compounds whose transition metal centers are insufficiently charged) can be generated by reacting with a rare earth element compound or a reaction product thereof with a Lewis base. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component.

As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used, as well as III, IV, 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, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, 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 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.

The component (C) used in the second polymerization catalyst composition is represented by the following general formula (i):
YR ¹ _a R ² _b R ³ _c (i)
[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. R ³ is a hydrocarbon group or a hydrogen atom, and 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 periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and 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]. Yes, the following general formula (X):
AlR ¹¹ R ¹² R ¹³ (X)
[Wherein, R ¹¹ and R ¹² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ¹³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹³ represents the above It may be the same as or different from R ¹¹ or R ¹² ]. Examples of the organoaluminum compound of the formula (X) 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, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organometallic compound as the component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  In the first production method of the block copolymer, as described above, the polymerization is carried out in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst composition is used. It can be carried out. Here, the method for producing the block copolymer includes, for example, (1) a component of a polymerization catalyst composition in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. May be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition 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 first production method of the block copolymer, the polymerization may be stopped using a polymerization terminator such as ethanol or isopropanol.

  In the first method for producing the block copolymer, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin 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. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10 Mpa is preferable. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, 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.

In the first method for producing the block copolymer, when the conjugated diene compound and the non-conjugated olefin are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol / l) at the start of the polymerization. l) is the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

Further, even if the first polymerization catalyst composition or the second polymerization catalyst composition is not used, that is, when a normal coordination ion polymerization catalyst is used, the monomer into the polymerization reaction system The block copolymer can be produced by adjusting the charging method. That is, the second production method of the block copolymer is characterized in that the chain structure of the copolymer is controlled by controlling the input of the conjugated diene compound in the presence of the non-conjugated olefin. The arrangement of the monomer units in the copolymer can be controlled. In addition, in this invention, a polymerization reaction system means the place where superposition | polymerization with a conjugated diene compound and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example.

Here, the charging method of the conjugated diene compound may be either continuous charging or split charging, and further, continuous charging and split charging may be combined. Moreover, continuous input is, for example,
Adding at a constant rate and for a fixed time.

Specifically, the concentration ratio of monomers in the polymerization reaction system can be controlled by dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin. As a result, it is possible to characterize the chain structure (that is, the arrangement of monomer units) in the resulting copolymer. Further, when the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer. The addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.

For example, when a block copolymer is produced by the above second production method, it is effective to continuously add a conjugated diene compound in the presence of the nonconjugated olefin to the polymerization reaction system in which the polymerization of the nonconjugated olefin has been started in advance. It becomes. In particular, when a multi-block copolymer is produced by the second production method, “a non-conjugated olefin is polymerized in a polymerization reaction system, and then the conjugated diene compound is reacted in the presence of the non-conjugated olefin. It is effective to repeat the operation of “continuous charging into the system” twice or more.

The second production method is not particularly limited as described above, except that the method of charging the monomer into the polymerization reaction system as described above. For example, the solution polymerization method, the suspension polymerization method, the liquid phase bulk polymerization method, Any polymerization method such as an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. In addition, the second production method is the same as the first production method, except that the method of charging the monomer into the polymerization reaction system as described above, and the conjugated diene compound as a monomer Non-conjugated olefins can be copolymerized.

In the second production method, it is necessary to control the input of the conjugated diene compound. Specifically, it is preferable to control the input amount of the conjugated diene compound and the input frequency of the conjugated diene compound. Examples of the method for controlling the introduction of the conjugated diene compound include a method of controlling by a program such as a computer and a method of controlling by analog using a timer or the like, but are not limited thereto. In addition, as described above, the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging. Here, when the conjugated diene compound is dividedly added, the number of times the conjugated diene compound is added is not particularly limited, but is preferably in the range of 1 to 5 times. If the conjugated diene compound is charged too many times, it may be difficult to distinguish it from a random copolymer.

In the second production method, since it is necessary that the non-conjugated olefin is present in the polymerization reaction system when the conjugated diene compound is charged, the non-conjugated olefin is continuously supplied to the polymerization reaction system. Is preferred. Moreover, the supply method of a nonconjugated olefin is not specifically limited.

［式中、Ｍ^１は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ａ及びＲ^Ｂは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^Ａ及びＲ^Ｂは、Ｍ^１及びＡｌにμ配位しており、Ｒ^Ｃ及びＲ^Ｄは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す］で表されるメタロセン系複合触媒、又は該メタロセン系複合触媒とホウ素アニオンとを含む重合触媒組成物の存在下、共役ジエン化合物と非共役オレフィンとを重合させることを特徴とする。 -Method for producing random copolymer-
Next, a method for producing the random copolymer will be described in detail. However, the manufacturing method described in detail below is merely an example.
The first production method of the random copolymer is represented by the following formula (A):
R _a MX _b QY _b (A)
[Wherein, R independently represents unsubstituted or substituted indenyl, R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2, preferably a metallocene composite catalyst represented by the following formula (XX):

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently represent a group having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. The conjugated diene compound and the non-conjugated olefin are polymerized in the presence of the metallocene composite catalyst represented by the above or a polymerization catalyst composition containing the metallocene composite catalyst and a boron anion.

According to the first production method, except that the metallocene composite catalyst or the polymerization catalyst composition is used, the conjugation which is a monomer is performed in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst. A diene compound and a non-conjugated olefin can be copolymerized, and the conjugated diene compound-non-conjugated olefin copolymer obtained in this way has a monomer unit of the non-conjugated olefin arranged completely irregularly. It has a random part. 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, cyclohexane, mixtures thereof etc. are mentioned.

The metallocene composite catalyst is a compound having a lanthanoid element, a scandium or yttrium rare earth element and a Group 13 element of the periodic table, and is represented by the above formula (A), preferably the above formula (I). It is characterized by. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

On the other hand, in the metallocene composite catalyst, the metal M ¹ in the formula (I) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferable examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (I), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton may 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 and 2-methylindenyl. Note that the two Cp ^Rs in formula (I) may be the same or different from each other.

In the above formula (I), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R ^B are μ-coordinated to M1 and Al. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (I), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

（式中、Ｍ^２は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ｅ〜Ｒ^Ｊは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^ＫＲ^ＬＲ^Ｍで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、^１Ｈ−ＮＭＲにより決定することが好ましい。 The metallocene composite catalyst is, for example, in a solvent, represented by the following formula (YY):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently has 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3, and a metallocene complex represented by AlR ^K R ^L R ^M It is obtained by reacting with. 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 or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR.

In the metallocene complex represented by the above formula (II), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (I). In the above formula (II), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (I).

The metallocene complex represented by the above formula (II) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. In addition, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the synthesis of the catalyst becomes easy. Furthermore, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (II) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases 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 above formula (II) may exist as a monomer, or may exist as a dimer or a multimer higher than that.

On the other hand, the organoaluminum compound used to produce the metallocene composite catalyst is AlR ^K.
Represented by R ^L R ^M, wherein, ^{R K} and ^{R L} are independently a monovalent hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, ^{R M} is a monovalent C1-20 Provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 2 to 50 times mol, and more preferably about 3 to 5 times mol for the metallocene complex.

  The polymerization catalyst composition contains the metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the polymerization catalyst composition, similarly to the metallocene composite catalyst, a conjugated diene compound-nonconjugated olefin copolymer having a random portion in which the monomer units of the nonconjugated olefin are completely irregularly arranged. However, since it further contains a boron anion, the content of each monomer component in the copolymer can be arbitrarily controlled.

Specific examples of the boron anion constituting the two-component catalyst in the polymerization catalyst composition include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundeborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

In addition, the said boron anion can be used as an ionic compound combined with the cation. Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation,
Examples include ferrocenium cations having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by 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. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In addition, it is preferable to add 0.1-10 times mole with respect to the said metallocene type composite catalyst, and, as for the ionic compound which consists of a boron anion and a cation, it is still more preferable to add about 1 time mole.

Preferred examples of the cocatalyst that can be used in the polymerization catalyst composition include an aluminoxane in addition to the organoaluminum compound represented by the above-described AlR ^K R ^L R ^M. The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.

  In the first method for producing the random copolymer, as described above, except for using the metallocene composite catalyst or the polymerization catalyst composition, a method for producing a polymer using a normal coordination ion polymerization catalyst; Similarly, polymerization can be carried out. Here, when the production method of the random copolymer uses the polymerization catalyst composition, for example, (1) a polymerization reaction system including a conjugated diene compound and a non-conjugated olefin as a monomer, The components may be provided separately and used as a polymerization catalyst composition in the polymerization reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. In addition, the usage-amount of the said metallocene type composite catalyst has the preferable range of 0.0001-0.01 times mole with respect to the sum total of a conjugated diene compound and a nonconjugated olefin.

  In the first method for producing the random copolymer, the polymerization may be stopped using a polymerization terminator such as ethanol or isopropanol.

  In the first method for producing a random copolymer, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin 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. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1 MPa-10 MPa is preferable. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, 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.

In the first method for producing a random copolymer, when the conjugated diene compound and the non-conjugated olefin are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol / l) at the start of the polymerization. l) is the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

Moreover, even if it does not use the said metallocene type composite catalyst or the said polymerization catalyst composition, the said random copolymer can be manufactured by adjusting the preparation method of the monomer in a polymerization reaction system. That is, the second production method of the random copolymer is characterized in that the chain structure of the copolymer is controlled by controlling the input of the conjugated diene compound in the presence of the non-conjugated olefin, thereby The arrangement of the monomer units in the copolymer can be controlled. In addition, in this invention, a polymerization reaction system means the place where superposition | polymerization with a conjugated diene compound and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example.

Here, the charging method of the conjugated diene compound may be either continuous charging or split charging, and further, continuous charging and split charging may be combined. Moreover, continuous input is, for example,
Adding at a constant rate and for a fixed time.

Specifically, the concentration ratio of monomers in the polymerization reaction system can be controlled by dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin. As a result, it is possible to characterize the chain structure (that is, the arrangement of monomer units) in the resulting copolymer. Further, when the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer. The addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.

For example, when a random copolymer is produced by the second production method, the polymerization reaction system in which the polymerization of the conjugated diene compound and the nonconjugated olefin is started, in the presence of the nonconjugated olefin,
It is effective to add a conjugated diene compound one or more times or continuously add a conjugated diene compound to a polymerization reaction system for polymerizing a conjugated diene compound and a non-conjugated olefin in the presence of the non-conjugated olefin. Become.

The second production method is not particularly limited as described above, except that the method of charging the monomer into the polymerization reaction system as described above. For example, the solution polymerization method, the suspension polymerization method, the liquid phase bulk polymerization method, Any polymerization method such as an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. In addition, the second production method is the same as the first production method, except that the method of charging the monomer into the polymerization reaction system as described above, and the conjugated diene compound as a monomer Non-conjugated olefins can be copolymerized.

In the second production method, it is necessary to control the input of the conjugated diene compound. Specifically, it is preferable to control the input amount of the conjugated diene compound and the input frequency of the conjugated diene compound. Examples of the method for controlling the introduction of the conjugated diene compound include a method of controlling by a program such as a computer and a method of controlling by analog using a timer or the like, but are not limited thereto. In addition, as described above, the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging. Here, when the conjugated diene compound is dividedly charged, the number of times the conjugated diene compound is charged is not particularly limited.

In the second production method, since it is necessary that the non-conjugated olefin is present in the polymerization reaction system when the conjugated diene compound is charged, the non-conjugated olefin is continuously supplied to the polymerization reaction system. Is preferred. Moreover, the supply method of a nonconjugated olefin is not specifically limited.

In addition, the second production method includes the first polymerization catalyst composition and the second polymerization in which the polymerization of the conjugated diene compound and the non-conjugated olefin is used in the production of the block copolymer from the viewpoint of efficiently performing the polymerization. It is preferable to carry out in the presence of the catalyst composition. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene etc. are mentioned.

<Rubber component>
There is no restriction | limiting in particular as said rubber component, According to the objective, it can select suitably, For example, the said block copolymer, the said random copolymer, natural rubber, various butadiene rubbers, various styrene-butadiene copolymers Rubber, isoprene rubber, butyl rubber, bromide of copolymer of isobutylene and p-methylstyrene, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber , Styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluoro rubber, urethane rubber ,etc It is below. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as content of the said block copolymer in 100 mass parts of said rubber components, Although it can select suitably according to the objective, 3 mass parts-95 mass parts are preferable, and 20 mass parts- 90 parts by mass is more preferable.
If the content of the block copolymer is less than 3 parts by mass, the characteristics of the present invention may be small or may not be exhibited, and if it exceeds 95 parts by mass, the workability deteriorates. There are things to do.
On the other hand, when the content of the block copolymer is within the more preferable range, it is advantageous in terms of workability and bending fatigue resistance.

There is no restriction | limiting in particular as content of the random copolymer in 100 mass parts of said rubber components, Although it can select suitably according to the objective, 3 mass parts-95 mass parts are preferable, and 10 mass parts-90 Part by mass is more preferable.
If the content of the random copolymer is less than 3 parts by mass, the workability may be deteriorated, and if it exceeds 95 parts by mass, the characteristics of bending fatigue resistance may be small.
On the other hand, when the content of the random copolymer is within the more preferable range, it is advantageous in terms of both workability and bending fatigue resistance.

  A reinforcing filler can be blended with the rubber composition as necessary. Examples of the reinforcing filler include carbon black and inorganic filler, and at least one selected from carbon black and inorganic filler is preferable.

<Inorganic filler>
The inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose.For example, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, Examples thereof include magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together.
In addition, when using an inorganic filler, you may use a silane coupling agent suitably.

There is no restriction | limiting in particular as content of the said reinforcing filler, Although it can select suitably according to the objective, 5 mass parts-200 mass parts are preferable with respect to 100 mass parts of rubber components.
If the content of the reinforcing filler is less than 5 parts by mass, the effect of adding the reinforcing filler may not be seen so much, and if it exceeds 200 parts by mass, the rubber filler is mixed with the reinforcing filler. There is a tendency that it does not get caught, and the performance as a rubber composition may be reduced.

<Crosslinking agent>
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur Compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents, sulfur and the like can be mentioned. Among them, sulfur-based crosslinking agents are more preferable as the rubber composition for tires.

There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of rubber components.
When the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking hardly proceeds, and when the content exceeds 20 parts by mass, the cross-linking tends to proceed during kneading with some cross-linking agents. Or the physical properties of the vulcanizate may be impaired.

<Other ingredients>
In addition, it is also possible to use a vulcanization accelerator in combination, and examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
If necessary, reinforcing agents, softeners, fillers, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, scorch prevention agents, Known materials such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use.

(Crosslinked rubber composition)
The crosslinked rubber composition of the present invention is not particularly limited as long as it is obtained by crosslinking the rubber composition of the present invention, and can be appropriately selected according to the purpose.
The crosslinking conditions are not particularly limited and may be appropriately selected depending on the intended purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.

(tire)
The tire of the present invention is not particularly limited as long as the rubber composition of the present invention or the crosslinked rubber composition of the present invention is used, and can be appropriately selected according to the purpose.
Examples of the application site in the tire of the rubber composition of the present invention or the crosslinked rubber composition of the present invention include, but are not limited to, a tread, a base tread, a sidewall, a side reinforcing rubber, and a bead filler. .
As a method for manufacturing the tire, a conventional method can be used. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.

(Applications other than tires)
In addition to tire applications, the rubber composition of the present invention or the crosslinked rubber composition of the present invention may be used for anti-vibration rubber, seismic isolation rubber, belts (conveyor belts), rubber crawlers, various hoses, Moran and the like. 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.

(Preparation Example 1)
After adding 160 ml of a toluene solution to a sufficiently dried 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container in a glove box under a nitrogen atmosphere. , 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 100 ml of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 90 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a copolymer A (block copolymer). The yield of the obtained copolymer A was 12.50 g.

(Preparation Example 2)
In a fully dry 2L stainless steel reactor, 28.0 g of 1,3-butadiene (0.52 m
After adding 700 ml of a toluene solution containing ol), ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, dimethylaluminum (
μ-dimethyl) bis (2-phenylindenyl) neodium [(2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe ₂ ] 400.0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph _{3 CB (C 6 F 5)} 4) were charged 200.0Myumol, and a catalyst solution dissolved in toluene 80 ml. Thereafter, the catalyst solution was taken out from the glove box, an amount of 390.0 μmol in terms of neodymium was added to the monomer solution, and polymerization was performed at room temperature for 120 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol. And vacuum-dried at 70 ° C. to obtain a copolymer B (random copolymer). The yield of the obtained copolymer B was 18.00 g.

  About the block copolymer A and the random copolymer B prepared as described above, and the obtained butadiene rubber (BR01, manufactured by JSR), the weight average molecular weight (Mw), the molecular weight distribution (Mw / Mn), The 2-vinyl bond amount (Vi (%)), ethylene content, cis-1,4 bond amount, and DSC curve were measured and evaluated by the following methods. The results are shown in Table 1.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC
/ HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (R
I)] with respect to monodisperse polystyrene, the polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.
(2) Microstructure (1,2-vinyl bond amount (Vi (%)), cis-1,4 bond amount)
The butadiene part in the block copolymer and random copolymer and the microstructure of the butadiene rubber (1,2-vinyl bond content) are determined by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm). Obtained from the integral ratio of 1,2-vinyl bond component (5.0-5.1 ppm) and the total butadiene bond component (5-5.6 ppm), the butadiene portion in the copolymer, and the microstructure of the butadiene rubber (Cis-1,4 bond content) was determined from the ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm) and the total amount of cis-1,4 bond component (26.5-27.5 ppm). It calculated | required from the integral ratio of the butadiene coupling | bonding component (26.5-27.5ppm + 31.5-32.5ppm). Table 1 shows calculated values of 1,2-vinyl bond amount (Vi (%)) and cis-1,4 bond amount (%).
(3) Content of ethylene-derived portion The content (mol%) of the ethylene-derived portion in the block copolymer and random copolymer was determined by ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). From the integral ratio of the total ethylene bond component (28.5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). Table 1 shows the ethylene content (mol%).
(4) DSC curve Differential scanning calorimetry (DSC) is performed according to JIS K 7121-1987, and DS
A C curve was drawn.

In the ¹³ C-NMR spectrum chart of the copolymer A in FIG. 3, a peak derived from the ethylene block portion is observed at 29.4 ppm, and in the DSC curve of the copolymer A in FIG. A crystallization temperature derived from a block portion composed of monomeric cis units of 1,3-butadiene and a crystallization temperature derived from a block portion composed of ethylene monomer units in the vicinity of 120 ° C. can be observed.
As mentioned above, it turns out that the copolymer A is a block copolymer of a high cis 1,3-butadiene and ethylene.
The copolymer A was analyzed for chain distribution by applying the ozonolysis-GPC method described in the literature ("Proceedings of the Society of Polymer Science, Vol. 42, No. 4, Page 1347"). The gel permeation chromatography was measured based on [GPC: Tosoh HLC-8121GPC / HT, column: Showa Denko GPC HT-803 × 2, detector: differential refractometer (RI), monodisperse polystyrene as a reference. The temperature was measured using 140 ° C.]. As a result, it was confirmed that the block ethylene component, that is, the polyethylene component having a number average molecular weight (Mn) of 1000 or more was 80% by mass or more and the copolymer A was a block copolymer with respect to the total ethylene component.
Moreover, it can be determined by the fact that the peak area of 80 ° C. or higher indicating the amount of the block polyethylene component occupies 80% or more of the total endothermic peak area at a temperature of 40 to 140 ° C. If the randomness is high, the excellent performance of the present invention cannot be obtained.

  The copolymer B was analyzed for the copolymer B by applying the ozonolysis-GPC method described in the literature ("Science of Polymer Science Vol. 42, No. 4, Page 1347"). The gel permeation chromatography was measured based on [GPC: Tosoh HLC-8121GPC / HT, column: Showa Denko GPC HT-803 × 2, detector: differential refractometer (RI), monodisperse polystyrene as a reference. The temperature was measured using 140 ° C.]. As a result, it was found that the block ethylene component, that is, the polyethylene component having a number average molecular weight (Mn) of 1000 or more is 10% by mass or less, that is, the randomness is high with respect to all ethylene components.

  Furthermore, in the DSC curve of the copolymer B in FIG. 2, a melting point peak near 50 ° C. derived from continuous alternating bonds and a melting point peak above 120 ° C. derived from a polyethylene block are not clearly recognized. From this, it was found to be a random copolymer.

(Examples 1-3 and Comparative Examples 1-3)
About Examples 1-3 and Comparative Examples 1-3, the rubber compound of the compounding prescription shown in Table 2 was prepared, and vulcanized rubber obtained by vulcanizing at 160 ° C. for 20 minutes, according to the following method: Roll workability and bending fatigue resistance (index) were measured.

<Roll processability>
The unvulcanized rubber compound was wound around an 8-inch open roll at 60 ° C., and the wound state was visually observed to evaluate the roll processability in the following two stages. The results are shown in Table 2.
○: Can be wound around the roll from the time the roll is fed ×: Not sticky and not wound on the roll, and cannot be rolled << Bend fatigue resistance (index) >>
In accordance with a flex crack test according to JIS-K6260, the crack growth property was tested using a dematcher flex crack tester. A specified crack was given, and the number of bendings required for the crack to grow by 1 mm was measured. The larger the index value, the better the bending fatigue resistance. In the table,> 200 indicates that the sample was not cut even when the comparative example 1 was subjected to repeated fatigue twice as many times.

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

Claims (15)

A block copolymer of a conjugated diene compound and a non-conjugated olefin;
A random copolymer in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged;
A rubber composition comprising:   The rubber composition according to claim 1, wherein a mass ratio of the block copolymer to the random copolymer is in a range of 95/5 to 5/95.   The rubber composition according to claim 1, wherein the block copolymer and the random copolymer have a cis-1,4 bond content of the conjugated diene compound-derived portion of 50% or more.   The block copolymer and the random copolymer have a content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in a conjugated diene compound-derived part of 5% or less. The rubber composition according to claim 1.   The rubber composition according to claim 1, wherein the content of the non-conjugated olefin-derived portion in the block copolymer is more than 0 mol% and 50 mol% or less.   The rubber composition according to claim 1, wherein the block copolymer and the random copolymer have a polystyrene-equivalent weight average molecular weight of 10,000 to 10,000,000.   The rubber composition according to claim 1, wherein the block copolymer and the random copolymer have a molecular weight distribution (Mw / Mn) of 10 or less.   The rubber composition according to claim 1, wherein the non-conjugated olefin is an acyclic olefin.   The rubber composition according to claim 1, wherein the non-conjugated olefin has 2 to 10 carbon atoms. The rubber composition according to claim 8 or 9, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The rubber composition according to claim 10, wherein the non-conjugated olefin is ethylene.   2. The rubber composition according to claim 1, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The rubber composition according to claim 1, comprising 5 to 200 parts by mass of a reinforcing filler and 0.1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the rubber component.   A crosslinked rubber composition obtained by crosslinking the rubber composition according to claim 1. A tire comprising the rubber composition according to claim 1 or the crosslinked rubber composition according to claim 14.

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