JP5997938B2 - Method for producing butadiene polymer and method for producing tire - Google Patents

Description

  The present invention relates to a butadiene polymer not using fossil resources as a starting material, a method for producing a butadiene polymer, a rubber composition using the butadiene polymer, and a tire using the rubber composition.

In recent years, a method for refining fuel oil from biological resources (so-called biomass) including plant resources has been proposed due to increasing demands for reducing fossil resource consumption and greenhouse gas emissions (patents) Reference 1). Such a fuel oil is called a biofuel, and since it does not increase the total amount of carbon dioxide emission, it is expected in the future as a substitute for a fuel oil derived from fossil resources.
Many compounds derived from fossil resources are used not only in the field of fuel oil but also in the fields of household appliances, household goods, automobiles and the like. As an example, the same applies to compounds such as butadiene used as the main raw material of acrylonitrile / butadiene / styrene copolymer resin (ABS resin), or the main raw material of synthetic rubber such as butadiene rubber, which is widely used as a material for automobile tires. In addition, there is a need for a production method that does not use fossil resources as starting materials.
Among butadiene rubbers, a butadiene polymer having a high cis-1,4-bond content in a butadiene monomer unit is excellent in mechanical properties, so that it can be used as a material for automobile tires. -A technique for producing a butadiene polymer having a high bond content is required (see Patent Document 2).

JP 2009-046661 A JP 2005-15590 A

  An object of the present invention is to provide a butadiene polymer that does not use fossil resources as a starting material, a method for producing the butadiene polymer, a rubber composition using the butadiene polymer, and a tire using the rubber composition.

The present invention
1. A butadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from biological resources including plant resources, the cis-1,4 bond content measured by Fourier transform infrared spectroscopy of the butadiene polymer A butadiene polymer having 98.0% or more,
2. 2. The butadiene polymer according to 1 above, wherein the butadiene polymer has a value of δ13C of −30 ‰ to −28.5 ‰, or −22 ‰ or more,
3. The butadiene polymer according to 1 or 2, wherein the butadiene polymer has a Δ14C value of −75 to −225 ‰,
4). The butadiene polymer according to any one of the above 1 to 3, wherein a value of δ13C of the butadiene polymer is in the range of −29.5 ‰ to −28.5 ‰.
5. The butadiene polymer according to any one of 1 to 4 above, wherein the value of δ13C of the butadiene polymer is in the range of −30 ‰ to −29 ‰.
6). The butadiene polymer according to any one of 1 to 5 above, wherein the butadiene polymer has a molecular weight of 1,000 to 5,000,000.
7). 7. A method for producing a butadiene polymer according to any one of 1 to 6, wherein a biobutadiene monomer is produced from a biological resource including a plant resource, and a polymerization catalyst is produced using the biobutadiene monomer. A method for producing a butadiene polymer in the presence of the butadiene polymer,
8). The method for producing a butadiene polymer according to 7 above, wherein the polymerization catalyst is a polymerization catalyst containing a rare earth element-containing compound,
9. The method for producing a butadiene polymer according to the above 7, wherein the polymerization catalyst is a metallocene polymerization catalyst,
10. The method for producing a butadiene polymer according to any one of the above 7 to 9, wherein the organic solvent is present in the presence of an organic solvent and the total amount of the biobutadiene monomer, the organic solvent, and the butadiene polymer. , A method for producing a butadiene polymer of less than 20% by mass,
11. The butadiene polymer according to any one of 7 to 10 above, wherein a butadiene copolymer is produced from a butadiene monomer containing the biobutadiene monomer and a monomer copolymerizable with the butadiene monomer. Production method,
12 Bio-ethanol is synthesized from bio-derived resources including plant resources, and the bio-butadiene monomer is brought into contact with the composite metal oxide containing at least magnesium and silicon as metal elements under heating. The method for producing a butadiene polymer according to any one of 7 to 11 above, wherein the butadiene polymer is produced using the biobutadiene monomer.
13. A rubber composition comprising the butadiene polymer according to any one of 1 to 6 above,
14 A tire comprising the rubber composition according to the above 13,
I will provide a.

  ADVANTAGE OF THE INVENTION According to this invention, the butadiene polymer which does not use a fossil resource as a starting material, the manufacturing method of a butadiene polymer, the rubber composition using this butadiene polymer, and the tire using this rubber composition can be provided. .

Hereinafter, a butadiene polymer according to an embodiment of the present invention will be described in detail.
[Butadiene polymer]
A butadiene polymer according to an embodiment of the present invention is a butadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including a plant resource, and the Fourier transform infrared of the butadiene polymer. It is a butadiene polymer having a cis-1,4 bond content of 98.0% or more as measured by spectroscopy. A rubber composition made of a butadiene polymer having a cis-1,4 bond content of 98.0% or more has excellent crack growth resistance, low heat buildup, and wear resistance.

  The butadiene polymer of the present invention contains a biobutadiene monomer synthesized from biological resources including plant resources, and the δ13C value of the butadiene polymer is −30 to −28.5 ‰, or −22 or more. It is desirable that Here, the value of δ13C of the butadiene polymer is measured by a stable isotope ratio measuring device.

δ13C represents the ratio of stable isotopes in the substance. δ13C is the ratio of ¹³ C to ¹² C in the target substance, and ¹³ C / ¹² C is compared to the isotope ratio in the standard sample (fossil of Cretaceous belemnite). This is an index indicating how much the deviation is, and this ratio is represented by ‰ (percentage). It means that the ratio of ¹³ C in a substance is so low that the value (negative value) of (delta) ^13C leaves | separates from zero.
Light isotopes are more diffusive and more reactive than heavy isotopes. For example, in the case of carbon atoms of carbon dioxide in the atmosphere taken into plants by photosynthesis, ¹² C is better than ¹³ C. It has been found that it is easily fixed in plants.
That is, the carbon atoms taken into the plant body have a relatively large amount of ¹² C and a smaller amount of ¹³ C than carbon atoms in the atmosphere. Therefore, the stable isotope ratio (δ13C) of carbon taken into the plant body is lower than the stable isotope ratio of carbon existing in the atmosphere.
This change in isotope ratio is called isotope fractionation and is represented by Δ13C (Δ13C is distinguished from δ13C).
Δ13C = (δ13C in the atmosphere) − (δ13C in the sample)
Therefore, the butadiene polymer-derived substance can be specified from the value of δ13C of the butadiene polymer.

  The value of δ13C of the butadiene polymer is preferably in the range of −21 ‰ to −12 ‰. The value of δ13C of the butadiene polymer is preferably in the range of −29.5 ‰ to −28.5 ‰. Further, the value of δ13C of the butadiene polymer is preferably in the range of −30 ‰ to −29 ‰.

Moreover, since the butadiene polymer of the present invention is obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including a plant resource, the value of Δ14C of the butadiene polymer is −75 to − 225 ‰ is desirable.
Here, the value of Δ14C of the butadiene polymer means that the value of Δ14C of the butadiene polymer means a ¹⁴ C concentration ( ¹⁴ when the sample carbon is δ13C = −25.0 ‰. AN). Note that, as described above for the butadiene polymer, the value of δ13C was measured by a stable isotope ratio measuring apparatus.
Δ14C can be calculated from the above-described value of δ13C as follows.
δ14C = [( ¹⁴ As− ¹⁴ AR) / ¹⁴ AR] × 1000 (1)
δ13C = [( ¹³ As− ¹³ APDB) / ¹³ APDB] × 1000 (2)
here,
¹⁴ As: ¹⁴ C concentration of sample carbon: ( ¹⁴ C / ¹² C) s or ( ¹⁴ C / ¹³ C) s
¹⁴ AR: ¹⁴ C concentration of standard modern carbon: ( ¹⁴ C / ¹² C) R or ( ¹⁴ C / ¹³ C) R
The ¹⁴ C concentration in the equation (1) is converted based on the following equation based on the measured value of δ13C.
^{14 AN = 14 As × (0.975} / (1 + δ13C / 1000)) 2 ( when using a ¹⁴ C / ¹² C as ¹⁴ As)
Or
^{14 AN = 14 As × (0.975} / (1 + δ13C / 1000)) ( when using ¹⁴ C / ¹³ C as ¹⁴ As)
From the above,
Δ14C = [( ¹⁴ AN− ¹⁴ AR) / ¹⁴ AR] × 1000 (‰) is calculated.

The value of Δ14C of the butadiene polymer is −75 to −225 ‰, which is a level equivalent to the current Δ14C of carbon in carbon dioxide in the atmosphere, and is included in the organic matter fixed in the existing growing plant body. Means carbon.
Since the half-life of radioactive carbon ¹⁴ C is about 5730 years, the carbon contained in the fossil resource contains almost no radioactive carbon ¹⁴ C. Δ14C of butadiene derived from fossil resources is about −1000 ‰.
Therefore, the butadiene polymer-derived substance can be specified by the Δ14C value of the butadiene polymer, the decay amount of radioactive carbon ¹⁴ C per gram per minute, or the value of δ13C. In this case, the decay value of radioactive carbon ¹⁴ C per gram per minute is 0.1 dpm / gC or more.

The molecular weight of the butadiene polymer can be 1000 to 5000000. Preferably, it is 100,000 to 500,000, More preferably, it is 150,000 to 300,000.
Moreover, it is preferable that the butadiene monomer used when manufacturing a butadiene polymer contains 10-100 mass% of biobutadiene monomers with respect to the total mass of a butadiene monomer.

<Biobutadiene monomer component>
The biobutadiene monomer component is obtained by synthesizing bioethanol synthesized from biological resources including plant resources as a starting material.

[Method of synthesizing biobutadiene monomer]
<Synthesis method>
A method for synthesizing a biobutadiene monomer using bioethanol synthesized from biological resources (biomass) including plant resources as a starting material will be described.
First, bioethanol is produced from biomass. The produced bioethanol is brought into contact with a composite metal oxide containing at least magnesium and silicon as metal elements under heating to produce a mixture containing a biobutadiene monomer component. A biobutadiene monomer component is extracted from this mixture, and a butadiene polymer is produced using the extracted biobutadiene monomer component.
In this synthesis method, the composite metal oxide acts as a catalyst. From the viewpoint of expressing good catalytic activity, the temperature when bioethanol is brought into contact with the composite metal oxide is preferably 350 ° C to 450 ° C.

(Production of bioethanol)
Examples of biological resources that can be used as raw materials for bioethanol include sugarcane, corn, sugar beet, cassava, beet, wood, and algae. Among these resources, it is preferable to use sugarcane, corn, and sugar beet that contain a large amount of sugar or starch from the viewpoint of production efficiency.

(Composite metal oxide)
The composite metal oxide contains at least magnesium and silicon as metal elements. Among these, it is preferable to use a silica-magnesia composite oxide synthesized by a sol-gel method. Usable metal elements include zinc, zirconium, copper, aluminum, calcium, phosphorus, tantalum and the like.

(Production method of composite metal oxide)
Examples of the method for producing the composite metal oxide include a sol-gel method and a method in which silica is mixed with an aqueous solution of a metal salt and supported by evaporation and drying.

(Contact reaction between bioethanol and mixed metal oxide)
For the contact reaction between the composite metal oxide and bioethanol, a generally known fixed bed gas flow-type catalytic reaction apparatus (for example, JP-A-2009-51760) can be used.
The composite metal oxide is filled in the reaction tube, heated as a pretreatment in a carrier gas atmosphere such as nitrogen gas, and then the temperature of the reaction tube is lowered to the reaction temperature. Thereafter, a predetermined amount of carrier gas and bioethanol are introduced. The biobutadiene monomer is separated from the gas produced by the reaction. As a separation method, the generated gas is passed through a cooled condenser to separate heavy impurities such as unreacted bioethanol and water, and then the reaction gas is bubbled into an organic solvent to remove the biobutadiene monomer. It is dissolved in a solvent and recovered as a solution. Light impurities such as ethylene and carrier gas N ₂ are passed through without being dissolved in the organic solvent and discharged from the solvent tank.

[Method for producing butadiene polymer]
The method for producing the butadiene polymer of the present invention will be described.
The method for producing the butadiene polymer of the present invention is not particularly limited, and any of a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method can be used, and a solution polymerization method is particularly preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form. As the polymerization method, any of a coordination polymerization method using a catalyst containing a rare earth element-containing compound or a metallocene catalyst as a polymerization initiator and an anionic polymerization method using an organometallic compound as a polymerization initiator can be used. A coordination polymerization method using a catalyst containing a rare earth element-containing compound or a metallocene catalyst as a polymerization initiator is preferred.

Next, the preferable catalyst used with the manufacturing method of the butadiene polymer of this invention is demonstrated.
<Metalocene catalyst>
Preferred metallocene catalysts used in the method for producing a butadiene polymer of the present invention are represented by the following general formula (I) and general formula (II), and the following general formula (III). It is preferable to use a half metallocene cation complex.

（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、

(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 metallocene complex represented by: L represents a neutral Lewis base; w represents an integer of 0 to 3;

（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、

(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).

（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、

(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. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A half metallocene cation complex represented by

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

In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; 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.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）

(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. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; 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) contains a bistrialkylsilylamide ligand [—N (SiR ₃ ) ₂ ]. The alkyl groups R (R ^{a to} R ^f in the general formula (I)) contained in the bistrialkylsilylamide are each independently an alkyl group having 1 to 3 carbon atoms, and 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 methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group; phenoxy group and 2,6-di- -tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

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

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

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

  In the general formula (III), X is 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 tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate is exemplified, and among these, tetrakis (pentafluorophenyl) borate is preferable.

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

  In addition, 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 be present as a monomer. It may exist as a body or higher multimer.

<Catalyst containing rare earth element-containing compound>
Next, a catalyst containing a rare earth element-containing compound can be given as a preferred catalyst together with the metallocene catalyst. Preferred catalysts containing a rare earth element-containing compound include (A) a compound containing a rare earth element having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base, and (B) an organoaluminum compound. And (C) a catalyst containing 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 is preferably used.
The rare earth element of atomic number 57 to 71 in the periodic table included in the component (A) is preferably neodymium, praseodymium, cerium, lanthanum, gadolinium, or a mixture thereof among the rare earth elements of atomic number 57 to 71, Neodymium is particularly preferred.

  The rare earth element-containing compound is preferably a salt soluble in a hydrocarbon solvent, and specifically includes the rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites. Of these, carboxylates and phosphates are preferable, and carboxylates are particularly preferable. Here, examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, -Monoolefins such as butene, 2-butene, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene, etc. A halogenated hydrocarbon is mentioned.

As the rare earth element carboxylate, the following general formula (V):
(R ⁴ -CO ₂ ) ₃ M ¹ (V)
(Wherein, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and M ¹ is a rare earth element having an atomic number of 57 to 71 in the periodic table). Here, R ⁴ may be saturated or unsaturated, is preferably an alkyl group or an alkenyl group, and may be linear, branched or cyclic. The carboxyl group is bonded to a primary, secondary or tertiary carbon atom. As the carboxylate, specifically, octanoic acid, 2-ethylhexanoic acid, oleic acid, neodecanoic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [trade names of Shell Chemical Co., Ltd. , A carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom] and the like. Among these, salts of 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, and versatic acid are preferable.

As the alkoxide of the rare earth element, the following general formula (VI):
(R ⁵ O) ₃ M ¹ (VI)
(Wherein, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and M ¹ is a rare earth element having an atomic number of 57 to 71 in the periodic table). The alkoxy group represented by R ⁵ O, 2-ethyl - hexyl alkoxy group, oleyl alkoxy group, stearyl alkoxy group, phenoxy group, and benzylalkoxy group. Among these, a 2-ethyl-hexylalkoxy group and a benzylalkoxy group are preferable.

  Examples of the rare earth element β-diketone complex include the rare earth element acetylacetone complex, benzoylacetone complex, propionitrileacetone complex, valerylacetone complex, and ethylacetylacetone complex. Among these, an acetylacetone complex and an ethylacetylacetone complex are preferable.

  Examples of the rare earth element phosphate and phosphite include the rare earth element, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl phosphate), bis (p-nonylphenyl) phosphate, phosphorus Acid bis (polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid mono-2-ethylhexyl 2-ethylhexylphosphonic acid mono-p-nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2 -Ethylhexyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphine Among these, the rare earth elements, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, bis A salt with (2-ethylhexyl) phosphinic acid is preferred.

  Among the rare earth element-containing compounds, neodymium phosphate and neodymium carboxylate are more preferable, and in particular, neodymium branching such as neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium versatate, etc. Carboxylate is most preferred.

  The component (A) may be a reaction product of the rare earth element-containing compound and a Lewis base. The reaction product has improved solubility of the rare earth element-containing compound in the solvent due to the Lewis base, and can be stably stored for a long period of time. In order to easily solubilize the rare earth element-containing compound in a solvent and to store stably for a long period of time, the Lewis base is used in a proportion of 0 to 30 mol, preferably 1 to 10 mol, per mol of rare earth element. Or as a mixture of the two or as a product obtained by reacting both in advance. Here, examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, and a monovalent or divalent alcohol.

  The rare earth element-containing compound as the component (A) described above or a reaction product of these compounds and a Lewis base can be used singly or in combination of two or more.

The component (B) of the catalyst system used for the production of the butadiene polymer of the present invention has the following general formula (VII):
AlR ¹ R ² R ³ ... (VII)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom,
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 . Examples of the organoaluminum compound of the formula (VII) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminum Umdihydride, isobutylaluminum dihydride, and the like can be given. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. The organoaluminum compound as component (B) described above can be used alone or in combination of two or more.

  The component (C) of the catalyst system used in the production of the butadiene-based polymer of the present invention is at least selected from the group consisting of Lewis acids, complex compounds of metal halides and Lewis bases, and organic compounds containing active halogens. It is a kind of halogen compound.

  The Lewis acid has Lewis acidity and is soluble in hydrocarbons. Specifically, 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 bromide Aluminum, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, Examples include antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, and silicon tetrachloride. Among these, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are preferable. Alternatively, a reaction product of an alkylaluminum and a halogen such as a reaction product of triethylaluminum and bromine can be used.

  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 Oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, and the like. 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 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced. Examples of the organic compound containing the active halogen include benzyl chloride.

  In addition to the above components (A) to (C), an organoaluminum oxy compound, so-called aluminoxane is preferably added as a component (D) to the catalyst system used for the production of the butadiene polymer of the present invention. . Here, examples of the aluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, chloroaluminoxane and the like. By adding aluminoxane as the component (D), the molecular weight distribution becomes sharp and the activity as a catalyst is improved.

  The amount or composition ratio of each component of the catalyst system is appropriately selected according to its purpose or necessity. Of these, the component (A) is preferably used in an amount of 0.00001 to 1.0 mmol, more preferably 0.0001 to 0.5 mmol, relative to 100 g of butadiene. When the amount of component (A) used is less than 0.00001 mmol, the polymerization activity is low, and when it exceeds 1.0 mmol, the catalyst concentration increases and a deashing step is required. Moreover, the ratio of (A) component and (B) component is molar ratio, (A) component: (B) component is 1: 1-1: 700, Preferably it is 1: 3-1: 500. Furthermore, the ratio of the halogen in the component (A) and the component (C) is in the molar ratio of 1: 0.1 to 1:30, preferably 1: 0.2 to 1:15, more preferably 1: 2. 0 to 1: 5.0. Moreover, the ratio of the aluminum in (D) component and (A) component is 1: 1-700: 1 by molar ratio, Preferably it is 3: 1-500: 1.

  Outside the range of these catalyst amounts or component ratios, it is not preferable because it does not act as a highly active catalyst or requires a step of removing the catalyst residue. In addition to the above components (A) to (C), the polymerization reaction may be carried out in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.

  The production of the catalyst is, for example, by dissolving the components (A) to (C) in a solvent and, if necessary, reacting with butadiene. In that case, the addition order of each component is not specifically limited, Furthermore, you may add an aluminoxane as (D) component. From the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period, it is preferable that these components are mixed in advance, reacted and aged. Here, the aging temperature is 0 to 100 ° C, and preferably 20 to 80 ° C. If the temperature is less than 0 ° C., the aging is not sufficiently performed. If the temperature exceeds 100 ° C., the catalytic activity is lowered and the molecular weight distribution is widened. The aging time is not particularly limited, and can be ripened by contacting in the line before adding to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient, and stable for several days.

<Polymerization method>
The polymerization method of the butadiene polymer of the present invention is preferably performed by solution polymerization. Here, in the case of solution polymerization, an inert organic solvent is used as the polymerization solvent. Examples of the inert organic solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, 1- Monoolefins such as butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chloro And halogenated hydrocarbons such as toluene. Among these, a C5-C6 aliphatic hydrocarbon and alicyclic hydrocarbon are especially preferable. These solvents may be used alone or in combination of two or more. The amount of the organic solvent used is preferably less than 20% by mass with respect to the total amount of the biobutadiene monomer, the organic solvent, and the butadiene polymer.

  The butadiene polymer may be produced either batchwise or continuously. In addition, in the production of the butadiene-based polymer, in order not to deactivate the catalyst and the polymer, consideration should be given as much as possible to avoid mixing of deactivating compounds such as oxygen, water and carbon dioxide gas into the polymerization reaction system. It is preferable to

  The butadiene polymer may be a copolymer produced from a biobutadiene monomer and a monomer copolymerizable with the biobutadiene monomer. As a monomer copolymerizable with a biobutadiene monomer, as a conjugated diene compound as a monomer, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3- Examples thereof include butadiene and 1,3-hexadiene. On the other hand, examples of the aromatic vinyl compound as a monomer include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like. In addition, the monomer copolymerizable with the biobutadiene monomer may be synthesized from biological resources including plant resources or may be derived from petroleum resources. Furthermore, a predetermined amount of a normal butadiene monomer that is not derived from bioethanol may be contained.

[Rubber composition]
The rubber composition of the present invention is not particularly limited as long as it contains the (co) polymer of the present invention, and can be appropriately selected according to the purpose, but rubber components other than the copolymer of the present invention, inorganic It preferably contains a filler, carbon black, a crosslinking agent, and the like.

<Rubber component>
The rubber component is not particularly limited and may be appropriately selected depending on the purpose. For example, the (co) polymer, natural rubber, epoxidized natural rubber, various butadiene rubbers, and various styrene-butadiene copolymers of the present invention are used. Polymer 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 Examples thereof include coalesced rubber, styrene-isoprene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, and urethane rubber. These may be used individually by 1 type and may use 2 or more types together.
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>
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, and a sulfur compound. Of these, a sulfur-based crosslinking agent is 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 progress during kneading with some cross-linking agents, The physical properties of the sulfide 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.

  Further, the rubber composition of the present invention or the crosslinked rubber composition of the present invention can be used for anti-vibration rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses, Moran, etc. in addition to tire applications. The rubber composition of the invention or the crosslinked rubber composition of the invention can be used.

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.
[Production example of biobutadiene copolymer]
<Manufacture of catalyst>
A silica-magnesia composite oxide synthesized by a sol-gel method was used as a catalyst. The synthesis method of this catalyst is as follows. First, Mg (OH) ₂ gel was synthesized by dropping 100 mL of a 14% aqueous ammonia solution into a solution of Mg (NO ₃ ) ₂ .6H ₂ O (64 g) dissolved in 100 mL of distilled water. On the other hand, Si (OH) ₄ gel was synthesized by dropping 12.5 mL of 1.38M nitric acid and 50 mL of 14% ammonia aqueous solution into a solution of Si (OC ₂ H ₅ ) ₄ (55 mL) dissolved in 150 mL of ethanol. The obtained Mg (OH) ₂ gel was subjected to suction filtration after washing with distilled water, and the Si (OH) ₄ gel was subjected to suction filtration after washing with ethanol. These two types of gels were mixed, and the mixed gel was air-dried, then dried at 80 ° C., 500 ° C., and calcined in an N ₂ atmosphere to produce a silica-magnesia composite oxide catalyst.

<Manufacture of biobutadiene monomer>
Bioethanol obtained by fermenting sugarcane, tapioca and corn starches with yeast was used as a starting material.
A biobutadiene monomer was produced by contacting the catalyst produced by the above method with the bioethanol.
As the reaction apparatus, a fixed bed gas flow type catalytic reaction apparatus (manufactured by Okura Riken Co., Ltd.) was used. The manufactured silica-magnesia composite oxide catalyst was filled in a quartz reaction tube, and was subjected to heat treatment at 500 ° C. for 2 hours in a carrier gas atmosphere (N ₂ ; gas flow rate 66 mL / min) as a pretreatment.
After completion of the pretreatment, the temperature of the catalyst tube was lowered to the reaction temperature, and bioethanol gas diluted with N ₂ was introduced. The reaction temperature at this time was 350 degreeC or 450 degreeC.
The mixture containing the biobutadiene monomer was recovered by performing the following separation operation on the gas generated by the reaction. First, the product gas was bubbled into hexane, so that the target biobutadiene monomer was dissolved in the solvent. The recovered butadiene solution was purified by drying to further remove impurities such as ethanol, acetaldehyde, diethyl ether, ethoxyethylene, and ethyl acetate.

(Polymer production example 1)
<Preparation of catalyst>
In a glass bottle with a rubber stopper having a volume of 100 mL that has been dried and purged with nitrogen, sequentially, 7.11 g of a cyclohexane solution of 1,3-butadiene (butadiene concentration: 15.2% by mass), a cyclohexane solution of neodymium neodecanoate (neodymium concentration) : 0.56 M) 0.59 mL, toluene solution (aluminum concentration: 3.23 M) of methylaluminoxane (MAO) [manufactured by Tosoh Finechem] 10.32 mL, hexane solution of diisobutylaluminum hydride [manufactured by Kanto Chemical Co., Ltd. 90M) 7.77 mL was added, and after aging at room temperature for 2 minutes, 1.45 mL of a hexane solution (0.95M) of diethylaluminum chloride [manufactured by Kanto Chemical Co., Inc.] was added, and aging was performed for 15 minutes with occasional stirring. The neodymium concentration in the catalyst solution thus obtained was 0.011 M (mol / L).

<Production of polymer A>
A glass bottle with a rubber stopper having a volume of about 1 L, which has been dried and substituted with nitrogen, is charged with a cyclohexane solution of 1,3-butadiene and dry cyclohexane derived from dry refined petroleum resources, respectively, and a cyclohexane solution of butadiene (butadiene concentration: 5 (0.0 mass%) was put in a state in which 400 g was charged, and it was sufficiently cooled in a 10 ° C. water bath. Next, 1.56 mL (0.017 mmol in terms of neodymium) of the catalyst solution prepared as described above was added, and polymerization was performed in a 10 ° C. water bath for 3.5 hours. Subsequently, 2 mL of an isopropanol solution (NS-5 concentration: 5% by mass) of the anti-aging agent 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to stop the reaction. Furthermore, after reprecipitation in an isopropanol solution containing a small amount of NS-5, the precipitate was dried by a conventional method to obtain a polymer A with a yield of almost 100%. The obtained polymer A had a number average molecular weight of 205000 and a molecular weight distribution of 2.3.

<Production of polymer B>
A polymer B was obtained in the same manner except that the 1,3-butadiene used in the preparation of the catalyst and the production of the polymer A was changed to the biobutadiene obtained in the production of the biobutadiene monomer. As for the molecular weight of the obtained polymer B, the number average molecular weight was 198,000, and the molecular weight distribution was 2.3.

から導かれるｅ、ｆ、ｇの値を用い、下記式（XI）、式（XII）、式（XIII）：
（シス−１，４結合含量）＝ｅ／（ｅ＋ｆ＋ｇ）×１００（％）・・・（XI）
（トランス−１，４結合含量）＝ｆ／（ｅ＋ｆ＋ｇ）×１００（％）・・・（XII）
（ビニル結合含量）＝ｇ／（ｅ＋ｆ＋ｇ）×１００（％）・・・（XIII）
に従ってシス−１，４結合含量、トランス−１，４結合含量及びビニル結合含量を求めた。なお、上記スペクトルの１１３０ｃｍ^-1付近の山ピーク値ａはベースラインを、９６７ｃｍ^-1付近の谷ピーク値ｂはトランス−１，４結合を、９１１ｃｍ^-1付近の谷ピーク値ｃはビニル結合を、７３６ｃｍ^-1付近の谷ピーク値ｄはシス−１，４結合を示す。
≪ブタジエン重合体の重要平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）≫
ゲルパーミエーションクロマトグラフィー（商品名「ＨＬＣ−８１２０ＧＰＣ」、東ソー社製）を使用し、検知器として示差屈折計を用いて、以下の条件で測定し、標準ポリスチレン換算値として算出した。
カラム；商品名「ＧＭＨ−ＸＬ」（東ソー社製） ２本
カラム温度；４０℃
移動相；テトラヒドロフラン
流速；１．０ｍｌ／ｍｉｎ
サンプル濃度；１０ｍｇ／２０ｍｌ [Evaluation method]
<Physical properties of butadiene polymer>
<< Microstructure [cis-1,4 bond content (%), 1,2-vinyl bond content (%)] >>
A Fourier transform infrared branch photometer (FT / IR-4100, manufactured by JASCO Corporation) was used, and measurement was performed using the determinant described below.
Using the carbon disulfide of the same cell as a blank, the FT-IR transmittance spectrum of a carbon disulfide solution of a butadiene polymer prepared to a concentration of 5 mg / mL was measured, and the peak value near 1130 cm ⁻¹ of the spectrum was measured. a, where the valley peak value near 967 cm ⁻¹ is b, the valley peak value near 911 cm ⁻¹ is c, and the valley peak value near 736 cm ⁻¹ is d, the following determinant (X):

Using the values of e, f, and g derived from the following formulas (XI), (XII), and (XIII):
(Cis-1,4 bond content) = e / (e + f + g) × 100 (%) (XI)
(Trans-1,4 bond content) = f / (e + f + g) × 100 (%) (XII)
(Vinyl bond content) = g / (e + f + g) × 100 (%) (XIII)
The cis-1,4 bond content, trans-1,4 bond content and vinyl bond content were determined according to In the above spectrum, the peak value a near 1130 cm ⁻¹ is the baseline, the valley peak value b near 967 cm ⁻¹ is the trans-1,4 bond, and the valley peak value c near 911 cm ⁻¹ is the vinyl bond. , A valley peak value d in the vicinity of 736 cm ⁻¹ indicates a cis-1,4 bond.
≪Ratio of important average molecular weight (Mw) and number average molecular weight (Mn) of butadiene polymer (Mw / Mn) ≫
Using gel permeation chromatography (trade name “HLC-8120GPC”, manufactured by Tosoh Corporation), a differential refractometer was used as a detector, and measurement was performed under the following conditions to calculate a standard polystyrene equivalent value.
Column: Trade name “GMH-XL” (manufactured by Tosoh Corporation) 2 Column temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Flow rate: 1.0 ml / min
Sample concentration: 10 mg / 20 ml

<Measurement of δ13C>
The value of δ13C of a butadiene polymer produced from ethanol derived from corn, sugarcane and tapioca was measured with a stable isotope ratio measuring device.

<Measurement of Δ14C>
As a starting material, the value of δ13C of a butadiene polymer produced from bioethanol obtained by fermenting sugarcane, tapioca and corn starch with yeast is measured with a stable isotope ratio measuring device, and according to the conversion method described above, Δ14C was calculated.

<Measurement of ¹⁴ C decay per gram per minute>
¹⁴ C decay per gram quantity value of butadiene polymer produced from corn, sugarcane, tapioca-derived ethanol was measured using accelerator mass spectrometry (AMS), liquid scintillation counting method (Liquid Scintillation Counting Method; It was measured by.

<Evaluation of crack growth resistance and low heat build-up of rubber composition>
Cracking resistance of a rubber composition containing a butadiene polymer obtained by polymerizing a biobutadiene monomer produced from bioethanol obtained by fermenting sugarcane, tapioca, and corn starch in yeast The low heat generation characteristic was measured by the following method.
The rubber composition of the present invention includes a rubber component containing the butadiene polymer, carbon black, vulcanizing agent, vulcanization accelerator, anti-aging agent, anti-scorching agent, softening agent, zinc oxide, stearic acid. A compounding agent usually used in the rubber industry such as a silane coupling agent can be appropriately selected and blended. In addition, the said rubber composition can be manufactured by mix | blending the various compounding agent suitably selected as needed with the rubber component, kneading | mixing, heating, extrusion, etc.

≪Crack growth resistance≫
A 0.5 mm crack was made in the center part of the JIS No. 3 test piece, fatigue was repeatedly given at a strain of 50 to 100% at room temperature, and the number of times until the sample was cut was measured. The value at each strain was determined and the average value was used. In Table 2, it represented with the parameter | index which sets the comparative example 1 which mix | blended the polymer A to 100. The larger the index value, the better the crack growth resistance.

≪Low heat generation (3% tan δ) ≫
A dynamic spectrometer (manufactured by Rheometrics, USA) was used, and measurement was performed under the conditions of tensile dynamic strain of 3%, frequency of 15 Hz, and 50 ° C. In Table 2, it represented with the parameter | index which sets the comparative example 1 which mix | blended the polymer A to 100. It shows that it is excellent in low exothermic property (low loss property), so that an index value is small.

≪Abrasion resistance≫
The amount of wear was measured at room temperature using a Lambourn-type wear tester, the reciprocal of the amount of wear was calculated, and each index was displayed as a comparative example. The larger the index value, the smaller the amount of wear and the better the wear resistance.

[Example 1, Comparative Example 1]
Using each of the polymers A and B, a rubber composition was prepared according to the formulation shown in Table 1, and vulcanized at 145 ° C. for 33 minutes to obtain a vulcanized rubber.
The physical properties of polymers A and B and the value of δ13C were measured by the above methods. Further, the crack growth resistance, low heat build-up (3% tan δ) and wear resistance of the obtained vulcanized rubber were measured according to the evaluation method described above. The results are shown in Table 2.

* 1: Nitrogen adsorption specific surface area of the carbon black used: 42 m ² / g
* 2: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., NOCRACK 6C
* 3: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, manufactured by Ouchi Shinsei Chemical Co., Ltd., NOCRACK 224
* 4: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ-G
* 5: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DM-P

The obtained polymer A had a cis-1,4 bond content of 98.43%, a trans 1,4-vinyl bond content of 1.44%, and Mw / Mn = 2.3.
Further, the obtained polymer B had a cis-1,4 bond content of 98.29%, a trans 1,4-vinyl bond content of 1.48%, and Mw / Mn = 2.3.
The obtained polymer A had a δ13C value of −23.00, and the polymer B had a δ13C value of −14.69.
Further, the value of Δ14C of the obtained polymer A was −1000 ‰, and the value of Δ14C of the polymer B was −100 ‰.
Further, the ¹⁴ A decay value per gram per minute amount of the polymer A obtained was 0.05 dpm / gC, and the ¹⁴ C decay per gram amount value of the polymer B was 0.2 dpm / g C. It was.
From the above results, the comparative example 1 using the polymer A derived from petroleum resources and the example 1 using the polymer B using biobutadiene monomer as raw materials are crack growth resistance and low exothermic property. It was also found that the wear resistance is comparable to the conventional product.

Claims (13)

Ri Na by polymerizing a bio-butadiene monomer which is synthesized from the resource from organisms including plant resources,
A method for producing a butadiene polymer having a cis-1,4 bond content of 98.0% or more as measured by Fourier transform infrared spectroscopy of the butadiene polymer ,
Synthesize bioethanol from biological resources including plant resources,
A biobutadiene monomer is produced by contacting the synthesized bioethanol with a composite metal oxide containing at least magnesium and silicon as metal elements synthesized by a sol-gel method under heating,
A method for producing a butadiene polymer, wherein a butadiene polymer is produced using the biobutadiene monomer in the presence of a polymerization catalyst. 2. The method for producing a butadiene polymer according to claim 1, wherein the value of δ13C of the butadiene polymer is −30 ‰ to −28.5 ‰, or −22 ‰ or more. The method for producing a butadiene polymer according to claim 1 or 2, wherein the value of Δ14C of the butadiene polymer is -75 to -225 ‰. The method for producing a butadiene polymer according to any one of claims 1 to 3, wherein a value of δ13C of the butadiene polymer is in a range of -29.5 ‰ to -28.5 ‰. The method for producing a butadiene polymer according to any one of claims 1 to 3 , wherein a value of δ13C of the butadiene polymer is in a range of -30 ‰ to -29 ‰. The number average molecular weight of the said butadiene polymer is 1000-5 million. The manufacturing method of the butadiene polymer in any one of Claims 1-5. The method for producing a butadiene polymer according to any one of claims 1 to 6, wherein the polymerization catalyst is a polymerization catalyst containing a rare earth element-containing compound. The method for producing a butadiene polymer according to any one of claims 1 to 6, wherein the polymerization catalyst is a metallocene polymerization catalyst. The method for producing a butadiene polymer according to any one of claims 1 to 8 , wherein the organic solvent is present in the presence of an organic solvent and the total amount of the biobutadiene monomer, the organic solvent, and the butadiene polymer. On the other hand, the manufacturing method of the butadiene polymer which is less than 20 mass%. The butadiene polymer according to any one of claims 1 to 9 , wherein a butadiene copolymer is produced from a butadiene monomer containing the biobutadiene monomer and a monomer copolymerizable with the butadiene monomer. Manufacturing method. The composite metal oxide is Mg (OH) ₂ Gel and Si (OH) ₄ The method for producing a butadiene polymer according to any one of claims 1 to 10, which is obtained by mixing and baking two kinds of gels together with a gel. The method for producing a butadiene polymer according to any one of claims 1 to 11, wherein a temperature at the time of contacting with the composite metal oxide is 350 to 450 ° C. A butadiene polymer is obtained by the method for producing a butadiene polymer according to any one of claims 1 to 12 , then a rubber composition containing the butadiene polymer is obtained, and then a tire is produced using the rubber composition. A method for manufacturing a tire to be manufactured.