JP6055204B2 - Modified diene polymer, method for producing modified diene polymer, rubber composition and tire - Google Patents

Description

  The present invention relates to a modified diene polymer obtained by polymerizing a monomer monomer that does not use fossil resources as a starting material, a method for producing a modified diene polymer, a rubber composition using the modified diene polymer, and the rubber composition. The present invention relates to a tire using a tire.

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.
Among the diene-based synthetic rubbers, various properties can be improved by using a modified diene polymer obtained by modifying the terminal with various functional groups as an automobile tire. For example, Patent Document 2, Patent Document 3, Patent It is known from Document 4 and Patent Document 5. These modified diene polymers are also required to be made from biological resources including plant resources, which are similarly renewable resources.

JP 2009-046661 A WO2006 / 093051 WO2006 / 112450 publication JP 2007-204584 A JP 2003-246816 A

  The present invention relates to a modified diene polymer obtained by polymerizing a monomer monomer that does not use fossil resources as a starting material, a method for producing a modified diene polymer, a rubber composition using the modified diene polymer, and the rubber composition. It is an object to provide tires using tires.

The present invention
1. A modified diene polymer obtained by polymerizing a biobutadiene monomer synthesized from biological resources including plant resources, a nitrogen atom derived from a functional group in the modified diene polymer, a tin atom, a silicon atom A modified diene polymer containing at least one atom selected from a sulfur atom and an oxygen atom,
2. 2. The diene polymer according to 1 above, wherein the value of δ13C of the modified diene polymer is −30 ‰ to −28.5 ‰, or −22 ‰ or more,
3. The diene polymer according to 1 or 2 above, wherein the value of Δ14C of the modified diene polymer is −75 to −225 ‰,
4). The diene polymer according to any one of the above 1 to 3, wherein the value of δ13C of the modified diene polymer is in the range of −29.5 ‰ to −28.5 ‰,
5. The diene polymer according to any one of 1 to 4 above, wherein the value of δ13C of the modified diene polymer is in the range of −30 ‰ to −29 ‰,
6). The diene polymer according to any one of 1 to 5, wherein the molecular weight of the modified diene polymer is 1000 to 5000000,
7). A method for producing the modified diene polymer according to any one of 1 to 5, wherein
Producing biobutadiene monomer from biological resources including plant resources,
The biobutadiene monomer is used for polymerization in the presence of a polymerization catalyst to produce a diene polymer, and then the diene polymer obtained is selected from nitrogen atom, tin atom, silicon atom, sulfur atom and oxygen atom A method for producing a modified diene polymer, wherein a modified monomer containing at least one atom is reacted;
8). The method for producing a modified butadiene polymer according to 7 above, wherein the polymerization is anionic polymerization or coordination polymerization, and a modifier is reacted with an active terminal of the obtained diene polymer.
9. The method for producing a modified diene polymer according to any one of the above 1 to 5, wherein the polymerization uses a modified polymerization initiator containing at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom. .
10. The method for producing a modified diene polymer according to 7 above, wherein the diene polymer and the modifier are reacted by graft polymerization,
11. A method for producing a modified diene polymer according to any one of 1 to 6 above, wherein a biobutadiene monomer, a nitrogen atom, a tin atom, a silicon atom, a sulfur atom, and an oxygen are derived from biological resources including plant resources. A method for producing a modified diene polymer comprising copolymerizing a modified monomer containing at least one atom selected from atoms;
12 The modified diene polymer according to any one of 7 to 11 above, wherein a diene copolymer is produced from a diene monomer containing the biobutadiene monomer and a monomer copolymerizable with the diene monomer. Manufacturing method,
13. 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 modified diene polymer according to any one of 7 to 12 above, wherein the modified diene polymer is produced using the biobutadiene monomer,
14 A rubber composition comprising the modified diene polymer according to any one of 1 to 6 above,
15. A tire comprising the rubber composition according to 14 above,
I will provide a.

  According to the present invention, a modified diene polymer obtained by polymerizing a monomer monomer that does not use fossil resources as a starting material, a method for producing a modified diene polymer, a rubber composition using the modified diene polymer, and the rubber A tire using the composition can be provided.

Hereinafter, the modified diene polymer according to the embodiment of the present invention will be described in detail.
[Modified butadiene polymer]
The modified diene polymer according to the embodiment of the present invention is a modified diene polymer obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including a plant resource, and the modified diene polymer in the modified diene polymer. It is a modified diene polymer containing at least one atom selected from a functional group-derived nitrogen atom, tin atom, silicon atom, sulfur atom and oxygen atom. A tire excellent in wear and the like can be obtained.

  The modified diene polymer of the present invention contains at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom derived from a functional group in the polymer. Is mainly obtained by inducing a functional group into an unmodified diene polymer.

  The modified diene polymer of the present invention is produced using a biobutadiene monomer synthesized from biological resources including plant resources, and the value of δ13C of the modified diene polymer is from −30 to − It is desirable that it is 28.5 ‰ or -22 or more. Here, the value of δ13C of the modified diene 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 substance derived from the modified diene polymer can be identified from the value of δ13C of the modified diene polymer.

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

Moreover, since the modified diene polymer of the present invention is obtained by polymerizing a biobutadiene monomer synthesized from a biological resource including plant resources, the value of Δ14C of the modified diene polymer is −75. It is desirable to be--225 ‰.
Here, the value of Δ14C of the modified diene polymer means that the value of Δ14C of the modified diene polymer means the ¹⁴ C concentration when the sample carbon is assumed to be δ13C = −25.0 ‰. The value is converted to ( ¹⁴ AN). Here, δ13C of the modified diene polymer is as described above, and the value of δ13C is 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 diene polymer is −75 to −225 ‰, which is the same level as Δ14C of carbon in carbon dioxide in the present air, 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 does not include radioactive carbon ¹⁴ C. Δ14C of butadiene derived from fossil resources is about −1000 ‰.
Accordingly, the diene polymer-derived substance can be specified by the Δ14C value of the diene polymer, the amount of decay 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 modified diene polymer of the present invention 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 10-100 mass% of biobutadiene monomers are contained with respect to the total mass of a diene 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 modified diene polymer]
A method for producing the modified diene polymer of the present invention will be described.
As a production method of the modified diene polymer of the present invention, an unmodified butadiene polymer is produced using the biobutadiene monomer described in the above description, and a nitrogen atom, a tin atom, a silicon atom, a sulfur atom, and an oxygen are produced. There is a method of reacting a modifier containing at least one atom selected from atoms.

<Method for producing unmodified diene polymer>
The method for producing the unmodified diene polymer is not particularly limited, and any of a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, and an emulsion 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 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.
Further, as the polymerization initiator used in the coordination polymerization method, a rare earth metal compound can be used, and neodymium, lanthanum, and gadolinium compounds are preferable.

  Moreover, it is also possible to synthesize transpolybutadiene by using a nickel-based catalyst or the like. It is also possible to produce syndiotactic-1,2-polybutadiene by the suspension polymerization method described in JP-A-9-20811. That is, in the presence of butadiene, a cobalt compound, a group I to III organometallic compound or a hydrogenated metal compound, and a compound selected from the group consisting of ketone, carboxylic acid ester, nitrile, sulfoxide, amide, and phosphoric acid ester are contacted. And a catalyst made of a compound (component B) selected from the group consisting of carbon disulfide, phenyl isothiocyanate and xanthogenic acid compounds, and the like. Alternatively, a solution polymerization method comprising a catalyst system comprising a soluble cobalt-organoaluminum compound-carbon disulfide-melting point regulator may be used. At the molecular end of such an unmodified butadiene polymer, there is an active metal site derived from the catalyst used.

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

<Method for producing modified diene polymer>
A method for producing the modified diene polymer of the present invention will be described.
The method for producing the modified diene polymer of the present invention is not particularly limited, but representatively, the following five methods can be mentioned.
(1) Modified terminal termination: polymerized in the presence of a polymerization catalyst to produce a diene polymer, and then the obtained diene polymer and at least one selected from nitrogen atom, tin atom, silicon atom, sulfur atom and oxygen atom A method of reacting with a denaturing agent containing any atom.
(2) Initiating terminal modification: A method of polymerizing the biobutadiene monomer using a modified polymerization initiator containing at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom.
(3) Main chain modification 1: A method in which a modified monomer containing at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom is copolymerized with the biobutadiene monomer. The modifying monomer may be randomly copolymerized or block copolymerized with the biobutadiene monomer.
(4) Main chain modification 2: A method in which a diene polymer is obtained by a polymerization reaction and then a modifier is grafted.
(5) Main chain modification 3: A method of converting a double bond portion between carbons of the butadiene polymer into an epoxy group or a thioepoxy group after obtaining a diene polymer by a polymerization reaction.
The above methods (1) to (5) may be performed singly or in combination.

In carrying out the above methods (1) to (5), an anionic polymerization method, a coordination polymerization method, and an emulsion polymerization method can be used.
In particular, the anionic polymerization method is preferably used when the above methods (1) to (5) are performed. The coordination polymerization method is preferably used when the above methods (1) and (3) to (5) are performed. And it is preferable to use an emulsion polymerization method when performing each method of said (3)-(5).

A method of reacting a modifier using the anionic polymerization method or the coordination polymerization method is disclosed in, for example, WO2006 / 093051. Japanese Patent Application Laid-Open No. 2003-246816 discloses a method of reacting a modifier using the above anionic polymerization method. A method of reacting a modifier with a coordination polymerization method is disclosed in WO2006 / 112450. And the method of making a modifier react with the emulsion polymerization method is disclosed by Unexamined-Japanese-Patent No. 2007-204584. The modifying agents disclosed in these publications can be the modifying agents used in the present invention.
The modifier used in the present invention is a modifier containing at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom, and an oxygen atom, and these modifiers have a function as a functional group. It will be a thing.

  Specific examples of the modifier used in the above methods (1) to (5) are as follows. Examples of the modifier containing a nitrogen atom include bis (diethylamino) benzophenone, dimethylimidazolidinone, N-methylpyrrolidone, 4 -Dimethylamino benzylidene aniline etc. are mentioned. By using these nitrogen-containing compounds as modifiers, functional groups containing nitrogen such as substituted and unsubstituted amino groups, amide groups, imino groups, imidazole groups, nitrile groups, and pyridyl groups are introduced into conjugated diene polymers. can do.

Moreover, the compound described below can be used as a modifier containing a silicon atom.
Examples of hydrocarbyloxysilane compounds include (thio) epoxy group-containing hydrocarbyloxysilane compounds such as 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, and (2-glycidoxyethyl) methyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Examples include 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, and those obtained by replacing the epoxy group in these compounds with a thioepoxy group. Among these, 3-glycidoxy Propyl trimethoxysilane and 3-glycidoxypropyl triethoxysilane are particularly preferred.

  In addition, as imine group-containing hydrocarbyloxysilane compounds, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxy Silyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and their triethoxy Examples include trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds corresponding to silyl compounds. Among these, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1 -Propanamine is particularly preferred.

  Examples of the imine (amidine) group-containing compound include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4,5-dihydro. Imidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl)- 4,5-dihydroimidazole and the like can be mentioned, and among these, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

  Examples of the isocyanate group-containing compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyltriisopropoxysilane. Of these, 3-isocyanatopropyltriethoxysilane is preferred.

  Further, examples of the hydrocarbyloxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxy Orchids, divinyl diethoxy silane and the like, and among them, tetraethoxysilane is particularly preferred.

  Specific examples of tin atom-containing modifiers include triphenyltin laurate, triphenyltin-2-ethylhexarate, triphenyltin naphthate, triphenyltin acetate, triphenyltin acrylate, and tri-n-butyltin. Laurate, tri-n-butyltin-2-ethylhexarate, tri-n-butyltin naphthate, tri-n-butyltin acetate, tri-n-butyltin acrylate, tri-t-butyltin laurate, tri-t-butyltin -2-ethyl hexatate, tri-t-butyltin naphthate, tri-t-butyltin acetate, tri-t-butyltin acrylate, triisobutyltin laurate, triisobutyltin-2-ethylhexarate, triisobutyltin naphthate , Triisobuty Tin acetate, triisobutyltin acrylate, triisopropyltin laurate, triisopropyltin-2-ethyl hexatate, triisopropyltin naphthate, triisopropyltin acetate, triisopropyltin acrylate, trihexyltin laurate, trihexyltin 2-ethyl hexatate, trihexyl tin acetate, trihexyl tin acrylate, trioctyl tin laurate, trioctyl tin-2-ethyl hexatate, trioctyl tin naphthate, trioctyl tin acetate, trioctyl tin acrylate, tri- 2-ethylhexyltin laurate, tri-2-ethylhexyltin-2-ethylhexarate, tri-2-ethylhexyltin naphthate, tri-2-ethylhexyl Tin acetate, tri-2-ethylhexyl tin acrylate, tristearyl tin laurate, tristearyl tin-2-ethyl hexatate, tristearyl tin naphthate, tristearyl tin acetate, tristearyl tin acrylate, tribenzyl tin laurate, tri Benzyl tin-2-ethyl hexatate, tribenzyl tin naphthate, tribenzyl tin acetate, tribenzyl tin acrylate, diphenyl tin dilaurate, diphenyl tin-2-ethyl hexatate, diphenyl tin distearate, diphenyl tin dinaphthate, diphenyl tin diacetate, Diphenyltin diacrylate, di-n-butyltin dilaurate, di-n-butyltin di-2-ethylhexarate, di-n-butyltin diste Allate, di-n-butyltin dinaphthate, di-n-butyltin diacetate, di-n-butyltin diacrylate, di-t-butyltin dilaurate, di-t-butyltin di-2-ethylhexarate, di-t- Butyltin distearate, di-t-butyltin dinaphthate, di-t-butyltin diacetate, di-t-butyltin diacrylate, diisobutyltin dilaurate, diisobutyltin di-2-ethylhexarate, diisobutyltin distearate, Diisobutyltin dinaphthate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate, diisopropyltin-2-ethylhexarate, diisopropyltin distearate, diisopropyltin dinaphthate, diisopropyl Pyrtin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexarate, dihexyltin distearate, dihexyltin dinaphthate, dihexyltin diacetate, dihexyltin diacrylate, di-2- Ethylhexyltin dilaurate, di-2-ethylhexyltin-2-ethylhexarate, di-2-ethylhexyltin distearate, di-2-ethylhexyltin dinaphthate, di-2-ethylhexyltin diacetate, di-2- Ethylhexyltin diacrylate, dioctyltin dilaurate, dioctyltin di-2-ethylhexarate, dioctyltin distearate, dioctyltin dinaphthate, dioctyltin diacetate, dioctyl Diacrylate, distearyltin dilaurate, distearyltin di-2-ethylhexarate, distearyltin distearate, distearyltin dinaphthate, distearyltin diacetate, distearyltin diacrylate, dibenzyltin dilaurate , Dibenzyltin di-2-ethylhexarate, dibenzyltin distearate, dibenzyltin dinaphthate, dibenzyltin diacetate, dibenzyltin diacrylate, phenyltin trilaurate, phenyltin tri-2-ethylhexarate , Phenyltin trinaphthate, phenyltin triacetate, phenyltin triacrylate, n-butyltin trilaurate, n-butyltin tri-2-ethylhexarate, n-butyltin trinaphthate, n- Butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2-ethyl hexatate, t-butyltin trinaphthate, t-butyltin triacetate, t-butyltin triacrylate, isobutyltin trilaurate , Isobutyltin tri-2-ethylhexarate, isobutyltin trinaphthate, isobutyltin triacetate, isobutyltin triacrylate, isopropyltin trilaurate, isopropyltin tri-2-ethylhexarate, isopropyltin trinaphthate, isopropyltin Triacetate, isopropyl tin triacrylate, hexyl tin trilaurate, hexyl tin tri-2-ethyl hexatate, hexyl tin trinaphthate, Siltin triacetate, hexyl tin triacrylate, octyl tin trilaurate, octyl tin tri-2-ethyl hexatate, octyl tin trinaphthate, octyl tin triacetate, octyl tin triacrylate, 2-ethylhexyl tin trilaurate, 2- Ethyl hexyl tin tri-2-ethyl hexatate, 2-ethyl hexyl tin trinaphthate, 2-ethyl hexyl tin triacetate, 2-ethyl hexyl tin triacrylate, stearyl tin trilaurate, stearyl tin tri-2-ethyl hexatate, stearyl tin tri Naphthate, stearyltin triacetate, stearyltin triacrylate, benzyltin trilaurate, benzyltin tri-2-ethylhexarate, benzyltin Rinafuteto, benzyl tin triacetate, and the like benzyl tin triacrylate.

  Diphenyltin bismethylmalate, diphenyltin bis-2-ethylhexarate, diphenyltin bisoctylmalate, diphenyltin bisoctylmalate, diphenyltin bisbenzylmalate, di-n-butyltin bismethylmalate, di-n-butyltin bis- 2-ethyl hexatate, di-n-butyltin bisoctyl malate, di-n-butyltin bisbenzyl malate, di-t-butyltin bismethyl malate, di-t-butyltin bis-2-ethylhexarate, di- -T-butyltin bisoctylmalate, di-t-butyltin bisbenzylmalate, diisobutyltin bismethylmalate, diisobutyltin bis-2-ethylhexarate, diisobutyltin bisoctylmalate, diisobutyltin bisbenzyl , Diisopropyltin bismethylmalate, diisopropyltin bis-2-ethylhexarate, diisopropyltin bisoctylmalate, diisopropyltin bisbenzylmalate, dihexyltin bismethylmalate, dihexyltin bis-2-ethylhexarate, Dihexyltin bisoctylmalate, dihexyltin bisbenzylmalate, di-2-ethylhexyltin bismethylmalate, di-2-ethylhexyltin bis-2-ethylhexarate, di-2-ethylhexyltin bisoctylmalate, Di-2-ethylhexyltin bisbenzylmalate, dioctyltin bismethylmalate, dioctyltin bis-2-ethylhexarate, dioctyltin bisoctylmalate, dioctyltin bisbenzylmalate , Distearyltin bismethylmalate, distearyltin bis-2-ethylhexarate, distearyltin bisoctylmalate, distearyltin bisbenzylmalate, dibenzyltin bismethylmalate, dibenzyltin bis -2-ethyl hexatate, dibenzyl tin bis octyl malate, dibenzyl tin bis benzyl malate, diphenyl tin bismethyl agitate, diphenyl tin bis-2-ethyl hexatate, diphenyl tin bis octyl agitate, diphenyl tin bis benzyl azate, di-n -Butyltin bismethyl agitate, di-n-butyltin bis-2-ethylhexate, di-n-butyltin bisoctyl agitate, di-n-butyltin bisbenzyl agitate, di-t-butyltin bisme Til agitate, di-t-butyltin bis-2-ethylhexaate, di-t-butyltin bisoctyl agitate, di-t-butyltin bisbenzyl agitate, diisobutyltin bismethyl agitate, diisobutyltin bis-2-ethylhexaate, Diisobutyltin bisoctyl agitate, diisobutyltin bisbenzyl agitate, diisopropyltin bismethyl agitate, diisopropyltin bis-2-ethylhexaate, diisopropyltin bisoctyl agitate, diisopropyltin bisbenzyl agitate, dihexyltin bismethylagitate, dihexyltin bis- 2-ethyl hexatate, dihexyl tin bismethyl agitate, dihexyl tin bisbenzyl agitate, di-2-ethylhexyl tin bi Methyl agitate, di-2-ethylhexyltin bis-2-ethylhexate, di-2-ethylhexyltin bisoctyl agitate, di-2-ethylhexyltin bisben-ethylhexyltin bisbenzyl agitate, dioctyltin bismethyl agitate, dioctyltin Bis-2-ethylhexaate, dioctyltin bisoctyl agitate, dioctyltin bisbenzyl agitate, distearyl tin bismethyl agitate, distearyl tin bis-2-ethylhexaate, distearyl tin bisoctyl agitate, distearyl tin bisbenzyl Agitate, dibenzyltin bismethyl agitate, dibenzyltin bis-2-ethylhexaate, dibenzyltin bisoctyl agitate, dibenzyltin bisbenzyl Agitated for, and the like.

  Further, diphenyltin maleate, di-n-butyltin maleate, di-t-butyltin maleate, diisobutyltin maleate, diisopropyltin maleate, dihexyltin maleate, di-2-ethylhexyltin maleate, dioctyltin maleate , Distearyl tin malate, dibenzyl tin malate, diphenyl tin agitate, di-n-butyl tin agitate, di-t-butyl tin agitate, diisobutyl tin agitate, diisopropyl tin agitate, dihexyl tin diacetate, di-2-ethylhexyl tin agitate , Dioctyltin agitate, distearyltin agitate, dibenzyltin agitate and the like.

  Specific examples of the modifier containing a sulfur atom include thioketene compounds such as ethylenethioketene, butylthioketene, phenylthioketene, and toluylthioketene, 2-thiophenecarbonitrile, 3-thiophenecarbonitrile, benzo [ b] thiophene-2-carbonitrile, benzo [b] thiophene-3-carbonitrile, isobenzo [b] thiophene-1-carbonitrile, isobenzo [b] thiophene-3-carbonitrile, naphtho [2,3-b] Examples include compounds having a heterocyclic group containing a sulfur atom such as thiophene-2-carbonitrile and naphtho [2,3-b] thiophene-3-carbonitrile, and thiirane compounds such as thiirane, methylthiirane, and phenylthiirane. It is done.

  Examples of the modifier containing an oxygen atom include epoxy compounds, such as ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, and epoxidized natural rubber.

  Furthermore, 1- (4-N, N-dimethylaminophenyl) -1-phenylethylene, 1- (4-N, N-diethylaminophenyl) -1-phenylethylene, 1- (4-N, N-dipropyl) Examples also include phenylethylene compounds such as aminophenyl) -1-phenylethylene, 1- (4-N, N-dibutylaminophenyl) -1-phenylethylene, and 1- (4-morpholinophenyl) -1-phenylethylene. Further, when a diphenylethylene derivative having two polar groups can be used in the same manner, the one having one polar group is industrially preferable because it has excellent solubility in a hydrocarbon solvent.

In the modification method using the emulsion polymerization reaction, an unmodified diene polymer is obtained in a latex state, charged into a reaction vessel, and reacted at 30 to 80 ° C. for 10 minutes to 7 hours, whereby an unmodified diene polymer is obtained. A modified diene polymer obtained by graft polymerization of the above modifier is obtained. Furthermore, the modified diene polymer is obtained by coagulating the latex of the modified diene polymer, washing it, and drying using a dryer such as a vacuum dryer, an air dryer, or a drum dryer. The coagulant used for coagulating the modified diene latex is not particularly limited, and examples thereof include acids such as formic acid and sulfuric acid, and salts such as sodium chloride. The amount of the modifying agent is preferably in the range of 0.01 to 5.0% by mass, more preferably in the range of 0.01 to 1.0% by mass with respect to the rubber component in the diene latex.
After this modification reaction, alcohol or the like can be added for the purpose of stopping a known anti-aging agent or polymerization reaction, if desired.
After the modification treatment in this way, a conventionally known post-treatment such as solvent removal can be performed to obtain the desired modified diene polymer.

  As the catalyst used in the anionic polymerization method, examples of the organic alkali metal include hydrocarbon compounds containing metals such as lithium, sodium, potassium, rubidium, and cesium. And lithium or sodium compounds having the following carbon atoms. Specific examples thereof include, for example, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2 -Butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, 4-cyclopentyllithium, 1,4-dilithiobutene-2, etc. are mentioned, but the reaction proceeds rapidly to give a polymer with a narrow molecular weight distribution. In terms, n-butyllithium or sec-butyllithium is preferable.

  The hydrocarbon solvent is one that does not deactivate the alkali metal catalyst, and the suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, particularly having 2 to 12 carbon atoms. Propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1 -Pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. Moreover, these solvents can be used in mixture of 2 or more types.

  In the production method, the active ends of the modified butadiene polymer obtained by modifying both ends with the above compound are terminated by addition of alcohols such as water, methanol, ethanol, propanol, and butanol, and further modified. May be.

  The modified diene polymer of the present invention 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. Further, a predetermined amount of a normal diene 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.

<Production of polymer A>
To an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene are added so as to be 60 g of 1,3-butadiene and 15 g of styrene, and 2,2-ditetrahydro After adding 0.36 mmol of furylpropane and 0.72 mmol of n-butyllithium (BuLi), a polymerization reaction was carried out in a hot water bath at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%.
Next, 0.65 mmol of N, N-bis (trimethylsilyl) -3-aminopropylmethyldiethoxysilane was added to the polymerization reaction system, and a modification reaction was further performed at 50 ° C. for 30 minutes. Thereafter, 0.5 ml of a 5 mass% isopropanol solution of 2,6-di-t-butyl-p-cresol was added to the polymerization reaction system to stop the polymerization reaction, followed by drying according to a conventional method to obtain a modified polymer A. Table 2 shows the number average molecular weight, the bound styrene content, and the bound vinyl content of the butadiene portion of the modified polymer A obtained.

<Production of polymer B>
A modified polymer B was obtained in the same manner except that 1,3-butadiene used in the production of the modified polymer A was changed to the biobutadiene obtained in the production of the biobutadiene monomer. Table 2 shows the number average molecular weight, the bound styrene content, and the bound vinyl content of the butadiene portion of the resulting modified polymer B.

[Evaluation method]
<Physical properties of styrene-butadiene copolymer>
≪Microstructure [bonded styrene content (%), 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 important average molecular weight (Mw) and number average molecular weight (Mn) of styrene-butadiene copolymer (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>
Crack resistance of a rubber composition containing a styrene-butadiene copolymer obtained by polymerizing a biobutadiene monomer produced from bioethanol obtained by fermenting sugarcane, tapioca, and corn starch in yeast. Growth and low heat generation characteristics were measured by the following methods.
The rubber composition of the present invention includes a rubber component containing the styrene-butadiene copolymer, carbon black, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an anti-scorching agent, a softening agent, and zinc oxide. The compounding agents normally used in the rubber industry such as stearic acid and silane coupling agents 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.

≪Mooney viscosity≫
In accordance with JIS K 6300-1, preheating was performed at 130 ° C. for 1 minute, and the subsequent 4-minute value was measured.

≪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. The Mooney viscosity, low exothermic property (3% tan δ) and abrasion 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 bound styrene content of 19.6% and a vinyl content of 57.4%.
Further, the obtained polymer B had a bound styrene content of 20.1% and a vinyl content of 56.7%.
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, Comparative Example 1 using the polymer A derived from petroleum resources and Example 1 using the polymer B derived from biobutadiene monomer are low in heat buildup and wear resistance. It turned out that it is not inferior to the conventional product.

Claims (11)

Ri modified diene polymer der obtained by polymerizing a bio-butadiene monomer which is synthesized from biological resources including plant resources, nitrogen atom, a tin atom derived from the functional group of the modified diene polymer, silicon atoms A method for producing a modified diene polymer containing at least one atom selected from a sulfur atom and an oxygen atom ,
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 under heating,
The biobutadiene monomer is used for polymerization in the presence of a polymerization catalyst to produce a diene polymer, and then the diene polymer obtained is selected from nitrogen atom, tin atom, silicon atom, sulfur atom and oxygen atom A method for producing a modified diene polymer, wherein a modifying agent containing at least one atom is reacted. 2. The method for producing a modified diene polymer according to claim 1, wherein the value of δ13C of the modified diene polymer is −30 ‰ to −28.5 ‰, or −22 ‰ or more. The method for producing a modified diene polymer according to claim 1 or 2, wherein the value of Δ14C of the modified diene polymer is -75 to -225 ‰. The method for producing a modified diene polymer according to any one of claims 1 to 3, wherein the value of δ13C of the modified diene polymer is in the range of -29.5 ‰ to -28.5 ‰. The method for producing a modified diene polymer according to any one of claims 1 to 3 , wherein the value of δ13C of the modified diene polymer is in the range of -30 ‰ to -29 ‰. The method for producing a modified diene polymer according to any one of claims 1 to 5, wherein the modified diene polymer has a number average molecular weight of 1,000 to 5,000,000. The method for producing a modified diene polymer according to any one of claims 1 to 6, wherein the polymerization is anionic polymerization or coordination polymerization, and a modifier is reacted with an active terminal of the obtained diene polymer. The modified diene polymer according to any one of claims 1 to 6, wherein the polymerization uses a modified polymerization initiator containing at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom. Method. Denatured di ene polymers method according to claim 1 is reacted by graft polymerizing the diene polymer and the modifying agent. A modified diene polymer obtained by polymerizing a biobutadiene monomer synthesized from biological resources including plant resources, a nitrogen atom derived from a functional group in the modified diene polymer, a tin atom, a silicon atom, a denaturation method for producing a diene polymer containing at least one atom selected from sulfur atom and oxygen atom,
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 under heating ,
Next, a method for producing a modified diene polymer comprising copolymerizing an organic alkali metal compound and a modified monomer containing at least one atom selected from a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom in a hydrocarbon solvent. The modified diene weight according to any one of claims 1 to 10 , wherein a diene copolymer is produced from a diene monomer containing the biobutadiene monomer and a monomer copolymerizable with the diene monomer. Manufacturing method of coalescence.