JP6074161B2 - Rubber composition and tire manufacturing method - 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. For example, butadiene and styrene copolymer resin (ABS resin) as the main raw material, or compounds such as butadiene used as the main raw material for synthetic rubber such as styrene and butadiene rubber, which are widely used as materials for automobile tires Similarly, there is a need for a production method that does not use fossil resources as starting materials.

JP 2009-046661 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 a biological resource including a plant resource, wherein the butadiene polymer has a Δ14C value of −75 to −225 ‰. Polymer,
[2] A butadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including a plant resource, and the amount of gram per ¹⁴ C decayed per gram of the butadiene polymer is 0. A butadiene polymer of 1 dpm / gC or more,
[3] The method for producing a butadiene polymer according to [1] or [2], wherein a mixture containing a biobutadiene monomer is produced from a biological resource including a plant resource, and the mixture is used to produce a butadiene polymer. A method for producing a butadiene polymer for synthesizing a coalescence,
[4] A butadiene copolymer obtained by copolymerizing a butadiene monomer and a monomer copolymerizable with the butadiene monomer, wherein the butadiene monomer is derived from a living organism including plant resources. A butadiene copolymer comprising a biobutadiene monomer synthesized from a resource, wherein the butadiene copolymer has a Δ14C value of −75 to −225 ‰,
[5] A butadiene copolymer obtained by copolymerizing a butadiene monomer and a monomer copolymerizable with the butadiene monomer, wherein the butadiene monomer is derived from a living organism including plant resources. A butadiene copolymer comprising a biobutadiene monomer synthesized from a resource, wherein the butadiene copolymer has a ¹⁴ C decay rate per gram amount value of 0.1 dpm / gC or more,
[6] A method for producing a butadiene copolymer according to the above [4] or [5], wherein a biobutadiene monomer is produced from a plant resource and a biological resource, the biobutadiene monomer, A method for producing a butadiene copolymer, wherein a butadiene monomer and a copolymerizable monomer are copolymerized;
[7] The method for producing a butadiene copolymer according to [6], wherein ethanol is synthesized from plant resources and biological resources, and the synthesized ethanol is heated and at least magnesium and silicon are added as metal elements. A butadiene copolymer in which a biobutadiene monomer is produced by contact with a composite metal oxide containing the copolymer and the biobutadiene monomer and a monomer copolymerizable with the biobutadiene monomer are copolymerized Manufacturing method,
[8] A rubber composition comprising the butadiene polymer of [1] or [2], or the butadiene copolymer of [4] or [5],
[9] A tire comprising the rubber composition of [8] above,
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 biological resources including plant resources, and the value of Δ14C of the butadiene polymer is -75 to -225 ‰.
Moreover, the butadiene polymer according to the 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 ¹⁴ C of the butadiene polymer. The decay value per gram per minute is 0.1 dpm / gC or more.

Here, the value of Δ14C of the butadiene polymer is a value converted to ¹⁴ C concentration ( ¹⁴ AN) when it is assumed that the sample carbon is δ13C = −25.0 ‰. In addition, 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)
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 (‰)

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, carbon contained in fossil resources does not include 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 amount of gram per minute per ¹⁴ C, or the value of δ13C.

The number average 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. The number average molecular weight of the butadiene polymer is a number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography and using a differential refractometer as a detector.
Moreover, it is preferable that 10-100 mass% of biobutadiene monomers are contained with respect to the total mass of a butadiene monomer.

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

[Production method of biobutadiene monomer]
<Manufacturing method>
A method for producing 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 production 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 reaction method can be used. For example, among the reaction methods disclosed in Japanese Patent Application Laid-Open No. 2009-051760, a reaction method using a fixed bed gas flow type catalytic reaction device is applicable.
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 is not particularly limited, and any of solution polymerization method, gas phase polymerization method, and bulk polymerization method can be used. Among these, the solution polymerization method is preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form. As a polymerization method, any of an anionic polymerization method using an organometallic compound as a polymerization initiator and a coordination polymerization method using a rare earth metal compound as a polymerization initiator can be used.
As the polymerization initiator used in the anionic polymerization method, an organic metal compound can be used, and the metal species is preferably one selected from alkali metals and alkaline earth metals, and alkali metals are particularly preferable. Lithium metal is preferred. As the polymerization initiator used in the coordination polymerization method, a rare earth metal compound can be used, and a lanthanum compound is preferable. Moreover, it is also possible to synthesize transpolybutadiene by using a nickel-based catalyst.

  It is also possible to produce syndiotactic-1,2-polybutadiene by the suspension polymerization method described in JP-A-9-020811. That is, in the presence of butadiene, a compound selected from the group consisting of a cobalt compound, a group I to III organometallic compound or a hydrogenated metal compound, and a ketone, carboxylic acid ester, nitrile, sulfoxide, amide, and phosphoric acid ester; Can be produced using a ripening liquid (component A) obtained by contacting the catalyst and a catalyst comprising a compound (component B) selected from the group consisting of carbon disulfide, phenyl isothiocyanate and xanthogenic acid compounds. Alternatively, a solution polymerization method comprising a catalyst system comprising a soluble cobalt-organoaluminum compound-carbon disulfide-melting point regulator may be used.

The butadiene polymer may be a copolymer synthesized from a biobutadiene monomer and a monomer copolymerizable with the biobutadiene monomer. Examples of monomers copolymerizable with the biobutadiene monomer include conjugated diene compounds and aromatic vinyl compounds. Examples of the conjugated diene compound include 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene and the like. In this embodiment, isoprene is excluded from the conjugated diene compound copolymerizable with the biobutadiene monomer.
Examples of the aromatic vinyl compound include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like.

  The monomer copolymerizable with the biobutadiene monomer may be either one synthesized from biological resources including plant resources or one derived from petrochemicals. Moreover, the normal butadiene monomer which is not derived from bioethanol may be contained in a predetermined amount.

[Rubber composition]
The rubber composition of the present invention contains the butadiene polymer of the present invention, and preferably further contains a rubber component other than the butadiene polymer of the present invention, an inorganic filler, carbon black, and other additives. The rubber composition should just contain the butadiene polymer of this invention, and components other than a butadiene polymer can be suitably selected according to the objective.
There is no restriction | limiting in particular in content of the butadiene polymer in the rubber composition of the butadiene polymer of this invention, According to the objective, it can select suitably. The content of the butadiene polymer is preferably 10% by mass or more.

<Rubber component>
There is no restriction | limiting in particular in the rubber component which can be mix | blended with the rubber composition of this invention, According to the objective, it can select suitably.
Examples of the rubber component include the butadiene polymer of the present invention, natural rubber, epoxidized natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubber, butyl rubber, and a copolymer of isobutylene and p-methylstyrene. Bromide, 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 Examples thereof include rubber, isoprene-butadiene 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.

<Reinforcing filler>
A reinforcing filler can be blended in 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.
There is no restriction | limiting in particular in an inorganic filler, According to the objective, it can select suitably. Examples of inorganic fillers include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and titanium. Examples include potassium acid 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 in content of a reinforcing filler, According to the objective, it can select suitably. The reinforcing filler is preferably contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the rubber component.
The effect which reinforces a rubber composition as content of a reinforcing filler is 5 mass parts or more is acquired. A rubber component and a reinforcing filler can be mixed as it is 200 mass parts or less, and the performance as a rubber composition can be improved.

<Other additives>
Other additives include vulcanization accelerators. As the vulcanization accelerator, compounds such as guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate and xanthate can be used.
If necessary, reinforcing agents, softeners, fillers, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, anti-scorch agents, UV rays Known agents such as an inhibitor, an antistatic agent, an anti-coloring agent and other compounding agents can be used according to the purpose of use.

[Crosslinked rubber composition]
The rubber composition of the present invention may contain a crosslinking agent in addition to the butadiene polymer of the present invention, a rubber component other than the butadiene polymer, an inorganic filler, carbon black, and other additives. The rubber composition can form a crosslinked crosslinked rubber composition.

<Crosslinking agent>
There is no restriction | limiting in particular in the crosslinking agent which can be used for preparation of a crosslinked rubber composition, According to the objective, it can select suitably. For example, sulfur crosslinking agent, organic peroxide crosslinking agent, inorganic crosslinking agent, polyamine crosslinking agent, resin crosslinking agent, sulfur compound crosslinking agent, oxime-nitrosamine crosslinking agent sulfur and the like can be mentioned. Among these, in the case of a rubber composition for tires, it is preferable to use a sulfur-based crosslinking agent.
There is no restriction | limiting in particular in content of a crosslinking agent, According to the objective, it can select suitably. The crosslinking agent is preferably contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
If content of a crosslinking agent is 0.1 mass part or more, it can bridge | crosslink so that a predetermined effect may be acquired. If it is 20 mass parts or less, it can prevent that a bridge | crosslinking advances during kneading | mixing, and will not impair the physical property of a vulcanizate.

[tire]
The tire of the present invention includes the rubber composition or the crosslinked rubber composition of the present invention. In the tire of the present invention, components other than the rubber composition or the crosslinked rubber composition can be appropriately selected depending on the purpose.
Examples of the application site of the rubber composition or crosslinked rubber composition of the present invention in a tire include treads, base treads, sidewalls, side reinforcing rubbers, and bead fillers. The application site is not limited to these.
The tire of the present invention can be manufactured using a conventional method. 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.
[Production example of biobutadiene polymer]
<Manufacture of catalyst>
A silica-magnesia composite oxide synthesized by a sol-gel method was used as a catalyst. The manufacturing 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 1.38 M nitric acid and 50 mL of 14% aqueous ammonia 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 kinds 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.

<Production 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 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 was 350 ° C. or 450 ° C.
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.

[Production of Polymer A]
A nitrogen-substituted 5 L autoclave was charged with a monomer solution in which 2.4 kg of cyclohexane and 300 g of 1,3-butadiene were dissolved in a nitrogen atmosphere. To the autoclave, as catalyst components, a cyclohexane solution of neodymium versatate (0.09 mmol), a toluene solution of methylaluminoxane (MAO, 3.6 mmol), diisobutylaluminum hydride (DIBAH, 5.5 mmol) and diethylaluminum chloride (0. (18 mmol) in toluene and 1,3-butadiene (4.5 mmol) were aged at 40 ° C. for 30 minutes, and a pre-prepared catalyst composition was charged, followed by polymerization at 60 ° C. for 60 minutes. 200 g of this polymer solution was extracted into a methanol solution containing 0.2 g of 2,4-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping and dried with a roll at 110 ° C. To obtain a polymer A.

[Production of polymer B]
According to the production of the polymer A, except that a monomer solution in which 300 g of a biobutadiene monomer produced based on the production example of the biobutadiene monomer was used instead of 300 g of 1,3-butadiene was used. Polymerization was performed to obtain a polymer B.

[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 by an infrared method (Morero method).
≪Ratio of weight 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 “GMHHXL” (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 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>
The following methods were used to measure the crack growth resistance and low heat build-up characteristics of rubber compositions containing biobutadiene monomer produced from bioethanol obtained by fermenting sugarcane, tapioca and corn starch in yeast. did.
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.

[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 the polymers A and B, the value of Δ14C, and the decay of ¹⁴ C per gram per minute were measured by the above method. Further, the crack growth resistance and low exothermic property (3% tan δ) 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 resulting polymer A had a cis-1,4 bond content of 96.3% and a 1,2-vinyl bond content of 0.63%. The ratio (dispersion ratio) between the weight average molecular weight and the number average molecular weight of the polymer A was Mw / Mn = 1.8.
Further, the obtained polymer B had a cis-1,4 bond content of 96.3% and a 1,2-vinyl bond content of 0.63%. The dispersion ratio of the polymer B was Mw / Mn = 1.8.
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 index of crack growth resistance and the index of 3% tan δ of the vulcanized rubber of Example 1 using the polymer B are the same values as those of the vulcanized rubber of Comparative Example 1 using the polymer A. It was found that the crack growth resistance and low heat build-up were comparable to conventional products.

Claims (5)

A method for producing a rubber composition containing a butadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including a plant resource,
Synthesizing bioethanol from biological resources including plant resources;
A step of preparing a mixture containing a bio-butadiene monomer by contacting a composite oxide of magnesia, - said bioethanol, synthesized silica by a sol-gel method
The step of polymerizing the biobutadiene monomer,
A method for producing a rubber composition using a butadiene polymer in which the butadiene polymer is a homopolymer of a butadiene monomer, and the value of Δ14C of the butadiene homopolymer is −75 to −225 ‰. A method for producing a rubber composition containing a butadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including a plant resource,
Synthesizing bioethanol from biological resources including plant resources;
A step of preparing a mixture containing a bio-butadiene monomer by contacting a composite oxide of magnesia, - said bioethanol, synthesized silica by a sol-gel method
The step of polymerizing the biobutadiene monomer,
The rubber composition using a butadiene polymer in which the butadiene polymer is a homopolymer of a butadiene monomer, and the butadiene homopolymer has a ¹⁴ C decay rate per gram amount per minute of 0.1 dpm / gC or more. Production method.   The manufacturing method of the rubber composition of Claim 1 or 2 using the butadiene polymer whose number average molecular weights of standard polystyrene conversion are 1000-5 million. The composite oxide of silica-magnesia synthesized by the sol-gel method is obtained by mixing and baking Mg (OH _{) 2} gel and Si (OH) ₄ gel . The manufacturing method of the rubber composition as described in above.   The manufacturing method of a tire which obtains a rubber composition with the manufacturing method of the rubber composition in any one of Claims 1-4, and manufactures a tire using the obtained rubber composition.