JP2018168245A - Polymer and manufacturing method therefor - Google Patents

Abstract

To provide a polymer extremely less in amount of remained metal residue and extremely less in remained insoluble gel component.SOLUTION: There is provided a conjugated diene-based block copolymer containing a conjugated diene-based polymer containing a conjugated diene compound unit or a polymer block containing the conjugated diene compound unit, and having content of metals in the polymer with weight average molecular weight of 10,000 to 1,000,000 of 0.10 mass.ppm to 30 mass.ppm and content of an insoluble gel component satisfying following conditions: (content of the insoluble gel component) the number of visible gel which is visually confirmed on a filter paper by aspiration filtering a solution of the polymer dissolved in an organic solvent by using the filter paper is 2 or less.SELECTED DRAWING: None

Description

  The present invention relates to a polymer and a method for producing the same.

  In recent years, thermoplastic elastomers, which are soft materials having rubber elasticity, do not require a vulcanization process, and can be molded and recycled in the same manner as thermoplastic resins, are widely used in a wide range of fields.

  For example, a polymer of a conjugated diene monomer such as 1,3-butadiene or isoprene, or a vinyl aromatic monomer such as styrene copolymerizable with the conjugated diene monomer and the conjugated diene monomer. The copolymer is very important as an impact-resistant transparent resin or a modifier for polyolefin and polystyrene resins.

  Moreover, the hydrogenated polymer obtained by adding hydrogen to the olefinic double bond portion contained in the conjugated diene polymer has a feature that it is excellent in weather resistance. Taking advantage of this feature, hydrogenated polymers are used in automobile parts, home appliance parts, electric wire coverings, medical parts, sundries, footwear and the like.

  Generally, the conjugated diene polymer is produced by living anionic polymerization using an alkyl lithium as an initiator. Further, in the case of obtaining a hydrogenated polymer, a hydrogenation reaction (hereinafter also referred to as “hydrogenation reaction”) is performed on the olefinic double bond portion after polymerization by using a Group VIII or Group IV metal as a catalyst. Do.

  Various methods for hydrogenating polymers having olefinic double bonds have been reported, for example, suitable reduction of group VIII metals of the periodic table, particularly nickel or cobalt compounds and alkylaluminum compounds. A hydrogenation method using a catalyst combined with an agent is known. In addition, a titanium compound which is a group IV metal of the periodic table, for example, a catalyst in which a suitable reducing agent such as a bis (cyclopentadienyl) titanium compound and an alkylaluminum compound is combined is used. A method for hydrogenating an unsaturated double bond of a coalescence is known.

  The hydrogenation reaction using a homogeneous catalyst can generally achieve a high hydrogenation rate and high reproducibility with a small amount of catalyst, but it is difficult to remove the catalyst residue remaining in the polymer solution after the hydrogenation reaction. . The metal component remaining in the polymer reacts with air or ultraviolet rays to cause oxidative degradation of the polymer and deterioration of the hue of the product. It is desirable. Generally, a homogeneous catalyst is difficult to physically decalcify by filtration after the reaction, and is required to be separated by washing with water or the like by increasing water solubility by a chemical reaction.

  Therefore, in order to solve this problem, several proposals have been made as a deashing method for metal species remaining in the polymer solution.

  For example, regarding removal of a periodic table VIII metal catalyst such as nickel, Patent Document 1 discloses a method of treating with an oxidizing agent and a dicarboxylic acid in order to remove residues, and Patent Document 2 discloses a method of treating oxidized metal with silica. A method of adsorbing on an acid salt to remove the catalyst is disclosed. Patent Document 3 discloses a method in which a nickel catalyst that has reacted with oxygen is adsorbed on activated carbon and removed. As for the method for removing the titanium residue, Patent Document 4 discloses a method of oxidizing metal species using excess hydrogen peroxide and washing with an aqueous polycarboxylic acid solution, or adding an aqueous polycarboxylic acid solution to chew. A method of efficiently removing most of the metal by highly mixing using a rotary disperser having a mating structure is disclosed.

US Pat. No. 4,595,749 US Pat. No. 5,104,972 US Pat. No. 5,089,541 WO2013161890

  However, the conjugated diene polymers produced by using these methods form a crosslinked structure between the polymers by uniformly oxidizing a part of the polymer structure with an oxidizing agent. There is a problem in diffusing into the coalescence solution as an insoluble component. Usually, these insoluble components are filtered by a strainer or the like and processed so as not to be mixed into the product. However, since the insoluble components frequently clog the filter, it is essential to clean the filter several times a day, and the production yield deteriorates due to the loss of the gelled polymer. Moreover, about the partially hydrogenated conjugated diene polymer, since many double bond parts rich in the reactivity with respect to an oxidation reaction remain | survive, the deashing operation using the above-mentioned oxidizing agent cannot be implemented.

  For this reason, a partially hydrogenated conjugated diene polymer having a low metal residue has not been industrially produced so far.

  Moreover, the technique described in Patent Document 4 describes a technique for reducing metal residues from the product. That is, it describes a technique for reducing metal residues from a product by using organic acid water. However, when the reaction solution is treated with organic acidic water without using an oxidizing agent, the metal species takes in a part of the polymer having a high molecular weight, condenses and solidifies, and is equivalent to the gel content at the interface between the organic phase and the aqueous phase. There is a problem of generating insoluble components over time. Since this insoluble component occurs after the rubber solution passes through the strainer, it can be removed by physical removal such as decantation, but it is often mixed in the product and deteriorates the product quality as an insoluble solid containing metal components. It becomes a factor to make. In addition, it is stated that the efficiency of demineralization can be increased by using hydrogen peroxide, etc., but since oxidizers with strong oxidizing power are used in large excess, aging added in the finishing process There is a problem that the inhibitor is colored by being oxidized and the color of the product is impaired, and an excessive burden is imposed on the manufacturing equipment. Similarly to the above, hydrogen peroxide oxidizes and crosslinks the remaining double bonds in the polymer molecule as an oxidant, and thus cannot suppress the generation of gel components.

  For this reason, there is a strong demand for a hydrogenated conjugated diene polymer having a very low color tone and a little metal residue remaining in the production process and product, and a production method thereof. .

  Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and an object thereof is to provide a polymer with a very small amount of remaining metal residue and a very small amount of remaining insoluble gel component. To do.

  As a result of intensive studies to solve the above problems, the present inventor has conjugated diene polymer containing a conjugated diene compound unit, or a conjugated diene block weight containing a polymer block containing a conjugated diene compound unit. When the metal content in the polymer having a weight average molecular weight of 10,000 to 1,000,000 is within a predetermined range, the amount of the remaining metal residue is extremely small, and the remaining insoluble gel component is extremely small. Found less.

  In addition, by using a production method having a predetermined process, the generation of insoluble gel components is controlled to an extremely small amount, and metal species are efficiently removed from the polymer solution. The inventors have found that a conjugated diene-based polymer containing almost no can be produced, and have completed the present invention.

That is, the present invention is as follows.
[1]
A conjugated diene polymer containing a conjugated diene compound unit, or a conjugated diene block polymer containing a polymer block containing a conjugated diene compound unit,
The metal content in the polymer having a weight average molecular weight of 10,000 or more and 1,000,000 or less is 0.10 mass ppm or more and 30 mass ppm or less,
The content of the insoluble gel component satisfies the following conditions:
Polymer:
(Content of insoluble gel component)
The polymer solution dissolved in the organic solvent is filtered off with a filter paper, and the number of visible gels visible on the filter paper is 2 or less.
[2]
The polymer is the conjugated diene block polymer,
The conjugated diene block polymer further contains a polymer block containing a vinyl aromatic hydrocarbon unit.
The polymer according to [1].
[3]
The total hydrogenation rate H of double bonds derived from the conjugated diene compound is 5.0% or more and 100% or less,
The polymer according to [1] or [2].
[4]
The metal is one or more organic salts or inorganic salts selected from the group consisting of titanium metals, lithium metals, aluminum metals, and nickel metals,
The polymer according to any one of [1] to [3].
[5]
A polymer containing a polymer containing a conjugated diene compound unit or a polymer block containing a conjugated diene compound unit, wherein the polymer has a weight average molecular weight of 10,000 to 1,000,000. , A method for producing a polymer that is 0.10 mass ppm or more and 30 mass ppm or less,
Having the following steps 1-5,
A method for producing a polymer.
Step 1: Step of preparing a polymer solution containing water and / or an organic solvent and lithium and / or titanium Step 2: Step of bringing the polymer solution into contact with an N-oxide compound Step 3: Step of the polymer solution and acid Step 4: Step of mixing the polymer solution Step 5: Step of removing water and / or organic solvent from the polymer solution [6]
In step 2, the molar ratio of the N-oxide compound to the lithium and / or titanium is 0.01 or more and 10 or less.
[5] The method for producing a polymer according to [5].
[7]
In step 3, the molar ratio of the acid to the lithium and / or titanium is 0.1 or more and 50 or less.
[5] The method for producing a polymer according to [6].

  According to the present invention, in a conjugated diene polymer, it is possible to provide a polymer having a small amount of remaining metal residue and a very small amount of remaining insoluble gel component, and a method for producing the same.

(A) is a side sectional view for explaining an example of a rotary disperser used in the present invention. 1 is a rotor and 2 is a stator. Further, (B) shows the meshing of 1 and 2 in a view seen from the entrance side.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

(Polymer)
The polymer of this embodiment is a conjugated diene polymer containing a conjugated diene compound unit or a conjugated diene block polymer containing a polymer block containing a conjugated diene compound unit. Further, the metal content in the polymer of the present embodiment having a weight average molecular weight of 10,000 to 1,000,000 is 0.10 mass ppm or more and 30 mass ppm or less. Furthermore, in the polymer of the present embodiment, the content of the insoluble gel component satisfies the following conditions.
(Content of insoluble gel component)
The polymer solution dissolved in the organic solvent is filtered off with a filter paper, and the number of visible gels visible on the filter paper is 2 or less.

<Conjugated diene polymer>
The conjugated diene polymer of this embodiment contains a conjugated diene compound unit. Here, the “conjugated diene compound unit” means a monomer unit contained in a polymer obtained by polymerizing a conjugated diene compound.

  Although it does not specifically limit as a conjugated diene compound, An aliphatic conjugated diene compound is mentioned, For example, 1, 3- butadiene, isoprene, piperylene, phenyl butadiene, 3, 4- dimethyl 1, 3- hexadiene, 4, Examples thereof include conjugated diene compounds containing 4 to 12 carbon atoms such as 5-diethyl-1,3-octadiene. Among these, 1,3-butadiene and isoprene are preferable. The conjugated diene polymer is a homopolymer obtained by polymerizing these one kind of conjugated diene compounds, or a copolymer obtained by polymerizing these two or more kinds of conjugated diene compounds.

  The homopolymer of a conjugated diene compound is a polymer mainly composed of a conjugated diene compound, but when the conjugated diene copolymer contains a compound other than the conjugated diene compound unit as a monomer unit, "Polymer" means that the content of one or more conjugated diene compound units in the copolymer is 5.0% by mass or more and 95% by mass or less. The structure of the copolymer is not particularly limited, but a random copolymer of a conjugated diene compound unit and one or more monomers copolymerizable with the conjugated diene compound is preferable.

<Conjugated diene block polymer>
The conjugated diene block polymer of this embodiment has a content of 5.0 to 95% by mass of one or more conjugated diene compound units, and is generally called a block copolymer. In particular, the structure is not limited. The conjugated diene-based block polymer includes one or more conjugated diene compound units formed by forming one or more polymer block structures in a conjugated diene copolymer in terms of the weight average molecular weight, Alternatively, the monomer unit derived from a compound copolymerizable with one or more conjugated diene compounds has a polymer block structure of 2,000 or more in terms of weight average molecular weight in the conjugated diene copolymer. It is preferable that it is formed and contained as described above.

  When one or both of the above polymer block structures are contained in a conjugated diene block polymer in combination of two or more polymer block structures, the weight average molecular weights of the respective polymer blocks are the same. Or different.

  When the polymer block structure is contained in one or more conjugated diene copolymers, a block polymer of one or more conjugated diene compounds and a block polymer of monomers copolymerizable with one or more conjugated diene compounds May be a structure linked by an arbitrary sequence, either a block polymer of one or more conjugated diene compounds or a block polymer of a compound copolymerizable with one or more conjugated diene compounds, or both May be a structure linked by a random copolymer of a conjugated diene compound and a compound copolymerizable with the conjugated diene compound. The block copolymer having such a structure may be a linear structure or a polymer having a geometric structure such as a graft structure or a star structure.

  A polymer obtained by copolymerization with a conjugated diene compound and a vinyl aromatic compound capable of copolymerization is one of the preferred embodiments of the conjugated diene polymer or the conjugated diene block polymer.

  The vinyl aromatic compound is not particularly limited. For example, styrene, α-methylstyrene, styrene substituted with an alkoxy group; 2-vinylpyridine, 4-vinylpyridine, vinylnaphthalene, vinyl substituted with an alkyl group. Examples include vinyl allyl compounds such as naphthalene. Of these, styrene and α-methylstyrene are preferred.

More preferable examples of the polymer block structure include the following structures.
A structure in which a block polymer of one aliphatic conjugated diene compound and a block polymer of one vinyl aromatic compound are linked. A block polymer of one aliphatic conjugated diene compound and the block weight A structure in which two block polymers of vinyl aromatic compounds are linked to both ends of the combination. Block polymer of any number of aliphatic conjugated diene compounds and any number of vinyl aromatic compounds. A structure in which a block polymer is linked in an arbitrary sequence, and both ends are block polymers of vinyl aromatic compounds. Block polymer of one aliphatic conjugated diene compound, and aliphatic A structure in which two random copolymers of a conjugated conjugated diene compound and a vinyl aromatic compound are linked, wherein both ends are random copolymers. One aliphatic conjugated die A structure in which a block polymer of a compound, two random copolymers of an aliphatic conjugated diene compound and a vinyl aromatic compound, and a block polymer of one vinyl aromatic compound are linked, Structure where one end is a random copolymer and one end is a block polymer of a vinyl aromatic compound

  In the conjugated diene polymer or the conjugated diene block polymer, the content of the vinyl aromatic compound is not particularly limited, but is 0% by mass or more and 50% by mass or less, and sufficient performance expression as a copolymer is obtained. Therefore, it is more preferably 5% by mass or more and 45% by mass or less, and further preferably 10% by mass or more and 40% by mass or less.

  The structure of the polymer of the present embodiment is not particularly limited, but may be a homopolymer when polymerized from one conjugated diene compound, and may be two or more conjugated diene compound units or one or more conjugated diene compound units. And a polymer comprising a polymer block mainly composed of a conjugated diene compound (a conjugated diene compound unit is 5.0% by mass or more and 95% by mass or less). Content rate).

  The polymer includes at least a polymer having a weight average molecular weight of 10,000 to 1,000,000. The weight average molecular weight of the polymer is preferably 50,000 or more and 500,000 or less, more preferably 60,000 or more and 400,000 or less, and further preferably 70,000 or more and 300,000 or less.

  Preferred examples of the conjugated diene block polymer include 1,3-butadiene, isoprene, piperylene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like. By copolymerizing such conjugated diene compounds containing 4 to 12 carbon atoms, more preferably 1,3-butadiene, isoprene, and vinyl aromatic compounds copolymerizable with any of these. It is a polymer obtained, and each monomer is the same component and contains a homopolymer block in the copolymer.

  When the conjugated diene polymer or conjugated diene block polymer is hydrogenated, the preferred weight average molecular weight is 10,000 or more and 1,000,000 or less, more preferably 50,000 or more and 500,000 or less, more preferably It is 60,000 or more and 400,000 or less, More preferably, it is 70,000 or more and 300,000 or less. The weight average molecular weight of the hydrogenated conjugated diene polymer or conjugated diene block polymer can be measured in terms of polystyrene using gel permeation chromatography (GPC) by the method described in the Examples described later.

  "Total hydrogenation rate H of double bond derived from conjugated diene compound" is the saturation generated from olefinically unsaturated double bond carbon in polymer and olefinically unsaturated double bond carbon by hydrogenation reaction It is a ratio of carbon, and is determined by a method for measuring the total hydrogenation rate H of double bonds derived from a conjugated diene compound, as shown below.

(Measurement of hydrogenation rate of conjugated diene compounds)
The hydrogenation rate of the unsaturated group of the conjugated diene compound can be measured under the following conditions by nuclear magnetic resonance spectrum analysis (NMR).

Prepare several samples of conjugated diene compounds with the same composition and the same molecular weight as the polymer for which the hydrogenation rate is determined, and adjust the hydrogenation rate to ¹ H-NMR measurement of conjugated diene compounds before and after hydrogenation. taking measurement. The rate of decrease of olefinic protons before and after hydrogenation is determined from the integral ratio of all protons bonded to the conjugated diene compound and olefinic protons of the conjugated diene compound, and the rate of decrease is calculated for each sample as the hydrogenation rate. A calibration curve is created from the integral ratio of all protons and olefinic protons in the conjugated diene compound and the hydrogenation rate obtained from the reduction rate. Using this calibration curve, the hydrogenation rate of the produced conjugated diene compound is determined. Using this calibration curve, as long as olefinic protons are observed as independent peaks from protons other than olefinic protons by ¹ H-NMR and the amount of protons can be quantified, structural differences such as random structure and block structure Therefore, the hydrogenation rate of a hydrogenated polymer having an unknown structure can be easily measured as long as it is a sample whose monomer composition and molecular weight have been analyzed in advance.

By adding a large amount of methanol to the reaction solution containing the conjugated diene compound before the hydrogenation reaction, the conjugated diene compound is precipitated and recovered. Subsequently, this conjugated diene compound is extracted with acetone, and the conjugated diene compound is vacuum-dried. Using this as a sample for ¹ H-NMR measurement, the olefinic proton content of the conjugated diene compound is measured.

By adding a large amount of methanol to the reaction solution containing the hydrogenated conjugated diene compound after the hydrogenation reaction, the hydrogenated conjugated diene compound is precipitated and recovered. Next, the hydrogenated conjugated diene compound is extracted with acetone, and the hydrogenated conjugated diene compound is vacuum-dried. This is used as a sample for ¹ H-NMR measurement to measure the hydrogenation rate.
The conditions for ¹ H-NMR measurement are described below.
Measuring instrument: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Measurement sample: Extracted sample before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

  The hydrogenation rate in the hydrogenated conjugated diene polymer or conjugated diene block polymer is not particularly limited, but is preferably 5.0% or more and 100% or less. In order to sufficiently obtain the characteristics, it is more preferably 20% or more and 98% or less, and further preferably 30% or more and 95% or less.

  The metal content (hereinafter also referred to as “metal residue amount”) in the polymer having a weight average molecular weight of 10,000 to 1,000,000 is preferably 0.10 mass ppm or more and 30 mass ppm or less. In order to obtain a product with excellent quality, it is more preferably 0.10 mass ppm or more and 10 mass ppm or less, and further preferably 0.1 mass ppm or more and 3.0 mass ppm.

  The content of the insoluble gel component contained in the polymer of this embodiment is such that a Buchner funnel equipped with 5A filter paper (for JIS P 3801 chemical analysis) is attached to a suction bottle with an internal volume of 2000 mL, and the pressure in the suction bottle is reduced to a vacuum pump. Is measured using a filtration device that is sucked under reduced pressure to 35 kPa. A solution prepared by dissolving 15 g of the polymer in 600 mL of toluene was subjected to suction filtration, and the time from the start of filtration until the liquid level gradually decreased until the surface of the filter paper was exposed from the liquid level was measured. After filtration, the filter paper is dried, the insoluble gel component remaining on the filter paper is stained with a staining solution, and the number of insoluble gel components having a diameter of 1 mm or more is measured using a digital microscope (VHX-6000). Can be determined by

  The content of the gel component in the polymer is 2 or less, preferably 0 to 1 from the viewpoint of reducing the content of insoluble impurities in product quality, and more preferably no insoluble gel component is confirmed after filtration. It is. The time required for filtration is preferably 0 to 60 seconds, more preferably 10 to 40 seconds, and further preferably 20 to 30 seconds from the viewpoint of reducing the amount of insoluble loose gel that cannot be visually confirmed in the product. is there.

[Components of metal residues]
As described above, since the insoluble gel component generated can be reduced to a very small amount, various metals that have been conventionally condensed together with the gel component and difficult to separate from the product as an insoluble metal can be specially used as a filter. The present inventors have found that the polymer solution can be separated with high efficiency without using a simple apparatus. Various metal components in a reduced state are oxidized by N-oxides to form water-soluble organic or inorganic salts, which can be separated into waste water by being water-solubilized in treated water. By relying on such a mechanism, the present inventor assumes that a metal component in a reduced state is not limited to a specific metal species and can be removed by the method of this embodiment.

  The amount of metal residue remaining in the polymer is not particularly limited as long as it is within the above-described content range, but the type, structure, and abundance of the metal component are not particularly limited. It is done. That is, the metal can be one or more organic salts or inorganic salts selected from the group consisting of titanium metals, lithium metals, aluminum metals, and nickel metals. These metals may be contained in the polymer as a catalyst or a dispersant in the polymer production process, but the concentration in the polymer can be reduced if the metal is in a reduced state. is there.

[Titanium metals]
The type of titanium metal is not particularly limited, but for example, crystalline titanium oxide such as rutile type, anatase type, brookite type, etc .: hydrous titanium oxide such as amorphous titanium oxide, orthotitanic acid and metatitanic acid; water Examples thereof include composite oxides of titanium and different metals such as titanium oxide and lithium titanate. Moreover, the organic titanium complex couple | bonded with ligands, such as various carboxylic acids, amino acids, alcohols, ketones, aldehydes, and organic phosphoric acids, by arbitrary number of coordination numbers may be sufficient.

[Lithium metals]
Although it does not specifically limit as a kind of lithium metal, Inorganic salts, such as lithium hydroxide and lithium carbonate; Complex oxides of lithium and a dissimilar metal like lithium titanate are mentioned. Further, it may be an organic lithium salt formed by neutralization or chelating bond with various carboxylic acids, amino acids, alcohols, ketones, aldehydes, organic phosphoric acids and the like at an arbitrary ratio.

[Aluminum metals]
Although it does not specifically limit as a kind of aluminum metal, Inorganic salts, such as aluminum hydroxide and aluminum carbonate; Complex oxide of aluminum and dissimilar metals like aluminum titanate are mentioned. Further, it may be an organoaluminum salt formed by neutralization or chelating bond with various carboxylic acids, amino acids, alcohols, ketones, aldehydes, organic phosphoric acids and the like at an arbitrary ratio.

[Nickel metals]
The kind of nickel metal is not particularly limited, and examples thereof include inorganic salts such as nickel hydroxide and nickel oxide; and composite oxides of nickel and different metals such as lithium nickelate. Further, it may be an organic nickel salt formed by neutralization or chelating bond with various carboxylic acids, amino acids, alcohols, ketones, aldehydes, organic phosphoric acids and the like at an arbitrary ratio.

[Analysis method of metal species and amount of metal]
Measurement is performed using inductively coupled plasma (ICP, Inductive Coupled Plasma, manufactured by Shimadzu Corporation, apparatus name: ICPS-7510). First, the polymer is completely dissolved in sulfuric acid and nitric acid, an aqueous solution containing metal components is sprayed into argon plasma, the intensity of the wavelengths of light unique to the various metal elements emitted from it is measured, and a calibration curve method is used. The amount of metal contained in the hydrogenated conjugated diene polymer is determined.

[Production method of polymer]
The method for producing a polymer according to this embodiment is a method for producing the polymer according to this embodiment, and includes the following steps 1 to 4.
Step 1: Step of preparing a polymer solution containing water and / or an organic solvent and lithium and / or titanium Step 2: Step of bringing the polymer solution into contact with an N-oxide compound Step 3: Step of the polymer solution and an acid Step 4: Step of mixing the polymer solution to obtain a mixed solution Step 5: Step of removing the aqueous phase and / or organic solvent from the mixed solution (polymer solution) to obtain a polymer Each step will be described in detail.

[Step 1]
Step 1 is a step of preparing a polymer solution containing lithium and / or titanium. The solvent of the polymer solution may be either an aqueous solvent or an organic solvent solvent, but an organic solvent solvent is preferable because a hydrogenation reaction can be performed directly without passing through a step of removing water from the polymer solution. The polymer concentration is preferably 5.0% by mass or more and 50% by mass or less from the viewpoint of product production efficiency and metal removal efficiency.

  The step of preparing the polymer solution is not particularly limited as long as it is a step of obtaining a solution containing the polymer of the present embodiment. For example, a conjugated diene polymer polymerized by a lithium polymerization catalyst is combined with a titanium compound and Examples include a method of preparing a hydrogenated conjugated diene copolymer solution by performing a hydrogenation reaction under a catalyst comprising various reducing agents.

  The polymer is not particularly limited as long as it is a polymer of the present embodiment, but specifically, a conjugated diene homopolymer having a molecular weight of 10,000 to 1,000,000 or a random of a conjugated diene compound and an aromatic vinyl compound. , Taper, block copolymer, and the like, and hydrogenation is possible to the unsaturated double bond of these conjugated diene units.

  The conjugated diene compound that can be used is not particularly limited. For example, 1,3-butadiene, isoprene, piperylene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3- Conjugated diene compounds containing 4 to 12 carbon atoms such as octadiene, preferably 1,3-butadiene and isoprene. The vinyl aromatic compound copolymerizable with the conjugated diene compound is not particularly limited. For example, styrene, α-methylstyrene, styrene substituted with an alkoxy group, 2-vinylpyridine, 4-vinylpyridine, vinylnaphthalene. A vinyl allyl compound such as vinyl naphthalene substituted with an alkyl group can be used, and styrene and α-methylstyrene are preferable.

  When a conjugated diene compound and a vinyl aromatic compound are mixed to produce a copolymer, the weight ratio is preferably 5:95 to 95: 5. When the amount of the conjugated diene compound used is 5% by weight or more, a copolymer having good impact resistance is obtained, and when it is 95% by weight or less, product processability tends to be good.

  Such a polymer is produced by a polymerization method generally used in the art, but it is preferable to perform anionic polymerization using an organolithium compound as an initiator. Specifically, n-butyl lithium, s-butyl lithium or the like can be used as the organic lithium compound. The amount of such an initiator used is generally used in this field, and can be freely adjusted according to the molecular weight of the target polymer. Thereafter, a hydrogenated conjugated diene polymer can be produced by performing a hydrogenation reaction on the obtained polymer solution.

  The titanium compound used in the hydrogenation reaction is not particularly limited as long as it is generally used in the art, but is a cyclopentadienyl titanium compound, for example, cyclopentadienyl titanium halide, cyclopenta Dienyl (alkoxy) titanium dihalide, bis (cyclopentadienyl) titanium dihalide, bis (cyclopentadienyl) titanium dialkylate, bis (cyclopentadienyl) titanium diallylide and bis (cyclopentadienyl) titanium It is selected from dialkoxy compounds and can be used alone or in combination.

  The titanium compound is preferably used in an amount of 0.01 to 20 mmol per 100 g of the conjugated diene polymer, more preferably 0.05 to 5 mmol per 100 g of the polymer. By making the use amount of the titanium compound 0.01 mmol or more, it is preferable in production from the viewpoint of the rate of hydrogenation reaction. It is preferable to maintain the above range since catalyst removal is not necessary after the reaction.

  The reducing agent used together with the titanium compound is not particularly limited as long as it is a reducing agent generally used in this field, but examples thereof include alkylaluminum compounds, alkylmagnesium compounds, organolithium compounds, and metal hydrides. It can also be used by combining multiple types.

  Although it does not specifically limit as a hydrogenation reaction using the said titanium-type catalyst, International patent application 00/08069, US Patent 4,501,857, 4,673,714, 4,980,421 No. 5,753,778, 5,910,566, 6,020,439 and the like.

  The hydrogenation reaction is carried out in an inert solvent, and the inert solvent means a solvent that does not react with any of the reactants of polymerization and hydrogenation reaction, specifically n-pentane, n-hexane, n-heptane, aliphatic hydrocarbons such as n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cycloheptane; and ethers such as diethyl ether and tetrahydrofuran can be selected from these. They can be used alone or in combination.

  The polymer concentration in the polymer solution in Step 1 is preferably 5.0% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 25% by mass or less. It is preferable for the polymer concentration to be in the above-mentioned range since the viscosity of the polymer solution can be adjusted to be easy to handle and the productivity is improved.

On the other hand, in the hydrogenation reaction, the polymer solution is maintained at a constant temperature in an inert gas atmosphere such as hydrogen, helium, argon, or nitrogen, and then a hydrogenation catalyst is added in a stirred or unstirred state, It is preferable to carry out by injecting at a constant pressure. Furthermore, the temperature of the hydrogenation reaction is preferably 30 to 150 ° C., and the pressure is preferably ^{2 to} 30 kg / cm ² .

When the temperature of the hydrogenation reaction is 30 ° C. or higher, the reactivity of the hydrogenation reaction is sufficiently high, so that a sufficient reaction yield can be obtained. Side reactions can be suppressed. When the pressure of the hydrogenation reaction is at 2 kg / cm ² or more, the reaction time because the reaction rate is sufficiently large is shortened, also possible to suppress the cost of investing in the reactor by the following 2~30kg / cm ² Economically preferable.

  Hereinafter, as a method for producing a hydrogenated conjugated diene polymer by removing residual metal from a polymer solution, for example, a conjugated diene polymer solution in which the hydrogenation reaction has been completed as described above, step 2 and step 3 will be described. explain.

[Step 2]
In step 2, the N-oxide compound is brought into contact with the polymer solution obtained in step 1. The mode of contact is not particularly limited, and the N-oxide compound may be added to the polymer solution, or the polymer solution may be added to the N-oxide compound or a solution thereof. More specifically, for example, a hydrogenated conjugated diene polymer solution, a non-carboxylic acid organic compound, and an N-oxide compound are added sequentially or mixed. Alternatively, it is a step of adding the N-oxide compound alone to the polymer solution or adding it as an aqueous solution.

  The non-acidic organic compound may be mixed and dissolved with N-oxide or added separately for the purpose of enhancing the solubility of the N-oxide compound in the polymer solution. Further, when the N-oxide is water-soluble, it may be added to the polymer solution as an aqueous solution. In addition, when the N-oxide compound can be handled in a liquid state at room temperature and atmospheric pressure, the N-oxide compound alone may be added to the polymer solution, and when it is easily dissolved in the polymerization solvent, the N of the polymerization solvent -You may add to a polymer solution as an oxide compound solution.

  When a non-carboxylic acid organic compound is used in this embodiment, at least one non-carboxylic acid organic compound selected from an alcohol compound, a ketone compound, an aldehyde compound, an acid anhydride compound, and an amine compound is added to the polymer solution. It is preferable to add.

(Non-carboxylic acid organic compound)
A non-carboxylic acid organic compound refers to a compound having no carboxyl group in the molecular structure. When a compound having a carboxyl group in the molecule is added before the N-oxide compound is brought into contact with the polymer solution or simultaneously with the N-oxide compound, the carboxyl group in the molecule associates between the N-oxide and the molecule, This is to significantly reduce the activity. The non-carboxylic acid organic compound is not particularly limited as long as it is a compound having no carboxyl group, but has a functional group such as an ester group, a ketone group, an alcohol group, an acid anhydride group or an amino group in the molecule. May be. The non-carboxylic acid organic compound is not particularly limited, but in addition to having a carboxyl group, the pKa value when dissolved in water is 5.0 or more, or the pKa value when dissolved in a DMSO solvent is 13. It is preferable to satisfy one of the conditions of 0 or more, and more preferable to satisfy both properties in order to maintain the activity of the N-oxaside compound. Although it does not specifically limit as a non-acidic organic compound, For example, the following is mentioned.

(Alcohol)
Examples of alcohols include methanol, ethanol, 1,2-ethanediol, propanol, 1,2-propanediol, 1,3-propanediol, glycerin, isopropanol, butanol, 1,2-butanediol, 1,3. -Butanediol, 1,4-butanediol, isobutanol, tert-butanol, pentanol, isopentanol, neopentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, cinnamyl alcohol, 1 -Dodecanol, 4-methoxybenzyl alcohol, perillyl alcohol, p-coumaryl alcohol, 2-phenylethanol, 1-undecanol, 1-phenylethanol, cumyl alcohol, benzyl alcohol, 1- Nonanol, 2-hydroxybenzyl alcohol, 1-O-hexadecyl-L-glycerol, sinapyl alcohol, 2-phenyl-1-propanol, 2-methyl-2-propen-1-ol, crotyl alcohol, (Z) -3 -Hexen-1-ol, 1-icosanol, 1-triaconethanol, 1-phenyl-2-methyl-2-propanol, vanillyl alcohol, furfuryl alcohol, 1-hexadecanol, 10-undecen-1-ol, 1-octadecanol, allyl alcohol, diacetone alcohol, caffeoyl alcohol, 3-phenyl-1-propanol, 2-methyl-2-butanol, 3-methoxybenzyl alcohol, 2-methoxybenzyl alcohol, 2-methyl-1 -Butanol, 2,2-dimethyl- 1-propanol, 3-methyl-2-buten-1-ol, gentisyl alcohol, 4- (chloromethyl) benzyl alcohol, 3-hydroxy-4-methoxybenzyl alcohol, peratryl alcohol, o-cumyl alcohol, linoleyl Examples include alcohol, hydroxymethyl mexiletine alcohol, and retinol.

(Esters)
Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, phenyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, phenyl propionate, hexyl propionate, butyric acid Methyl, ethyl butyrate, propyl butyrate, butyl butyrate, hexyl butyrate, phenyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, phenyl valerate, methyl caproate, ethyl caproate, propyl caproate, capron Butyl acid, hexyl caproate, phenyl caproate, methyl enanthate, ethyl enanthate, propyl enanthate, butyl enanthate, hexyl enanthate, phenyl enanthate, methyl caprylate, ethyl caprylate, propyl caprylate Butyl caprylate, hexyl caprylate, phenyl caprylate, methyl pelargonate, ethyl pelargonate, propyl pelargonate, butyl pelargonate, hexyl pelargonate, phenyl pelargonate, methyl caprate, ethyl caprate, propyl caprate, capric acid Butyl, hexyl caprate, phenyl caprate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, hexyl laurate, phenyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, Hexyl myristate, phenyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, hexyl palmitate, phenyl palmitate, Methyl lugarate, ethyl margarate, propyl margarate, butyl margarate, hexyl margarate, phenyl margarate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, hexyl stearate, phenyl stearate, benzoic acid Methyl, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, hexyl crotonate, phenyl crotonate, methyl valmitoleate, ethyl valmitoleate, Propyl valmitoleate, butyl valmitoleate, hexyl valmitoleate, phenyl valmitoleate, methyl oleate, ethyl oleate, propyl oleate, butyl oleate Chill, hexyl oleate, phenyl oleate, methyl vaccenate, ethyl vaccenate, propyl vaccenate, butyl vaccenate, hexyl vacsenate, phenyl vaccenate, methyl linoleate, ethyl linoleate, propyl linoleate, butyl linoleate Hexyl linoleate, phenyl linoleate, methyl linolenate, ethyl linolenate, propyl linolenate, butyl linolenate, hexyl linolenate, phenyl linolenate, methyl stearate, ethyl stearate, propyl stearate, butyl stearidate, stearidonic acid Hexyl, phenyl stearidonic acid, methyl stearidonic acid, ethyl stearidonic acid, propyl stearidonic acid, butyl stearidonic acid, hexyl stearidonic acid, phenyl stearidonic acid, Dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, trimethyl tricarbarate, triethyl tricarbarate, trimethyl trimellitic acid, trimellitic acid Examples include triethyl, methyl 2-ketopropionate, methyl 2-ketobutyrate, methyl acetoacetate, methyl lactate, ethyl lactate, trimethyl citrate, triethyl citrate, dimethyl tartrate, diethyl tartrate, and dibutyl tartrate.

(Ketones)
Examples of ketones include acetone, hydroxyacetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3- Octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-decanone, acetophenone, diacetyl, acetylacetone, 2,5-hexadione, Zimedone.

(Aldehydes)
Examples of aldehydes include acetaldehyde, propionaldehyde, isobutyraldehyde, benzaldehyde, pivalaldehyde, glyoxal, butyraldehyde, 3,3-dimethylbutyraldehyde, isovaleraldehyde, heptanal, hexanal, valeraldehyde, crotonaldehyde, decanal, Methacrolein, n-octanal, dodecanal, 3-methyl-2-butenal, tetradecanal, acrolein, glutaraldehyde, bromare, chloral, cis-4-heptenal, cyclohexanecarboxaldehyde, trans, cis-2,6-nonaldi Enal, 3,7-citronellal.

(Acid anhydrides)
Examples of the acid anhydrides include acetic anhydride, succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, decyl succinic anhydride, n-octyl succinic anhydride, dodecyl succinic anhydride. , Itaconic anhydride, allyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, (2-methyl-2- Propenyl) succinic anhydride, 2-buten-1-yl succinic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride, 2-hexen-1-yl succinic acid Anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 2-octenyl succinic anhydride, (2,7-octadie -1-yl) succinic anhydride, O-acetyl-malic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Acid anhydride, 2-dodecene-1-yl succinic anhydride, tetrafluorosuccinic anhydride, caronic acid anhydride, (+)-diacetyl-L-tartaric anhydride, (-)-diacetyl-D-tartaric anhydride 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, cis-4-cyclohexene-1, 2-dicarboxylic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2 3-dicarboxylic anhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, phenylsuccinic acid anhydride, 3,4-thiophene dicarboxylic acid anhydride, het acid anhydride, 4- (2,5-dioxotetrahydrofuran-3- Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, phthalic anhydride, 4-fluorophthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,2- Naphthalic anhydride, 4,4′-biphthalic anhydride, 4-methylphthalic anhydride, 3-methylphthalic anhydride, pyromellitic anhydride, 4-tert-butylphthalic anhydride, 3,3 ′, 4 4'-benzophenonetetracarboxylic dianhydride, 4- (1-propynyl) phthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4- (ethyne- 1,2-diyl) diphthalic anhydride, (1β, 4β) -bicyclo [2,2,1] hept-5-ene-2α, 3α-dicarboxylic anhydride, valeric anhydride, pentafluoropropionic anhydride And [3- (trimethoxysilyl) propyl] succinic anhydride.

(Amines)
Examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, ethylenediamine, hexamethylenediamine, hexamethyleneimine, N-methylhexamethyleneimine, triethylamine, N-cyclohexylamine, N, N-cyclohexylmethylamine. N, N-dimethyldodecylamine, aniline, N, N-dimethylaniline, piperidine, N-methylpiperidine, piperidone, N-methylpiperidone, piperazine, N-methylpiperidine, morpholine, N-methylmorpholine, 2,2,6 , 6-Tetramethyl N-methylmorpholine, pyrrole, N-methylpyrrole, pyridine, α-picoline, pyridazine, pyrimidine, 1,3,5-triazine, imidazole, N-methylimida , Pyrazole, N-methylpyrazole, oxazole, thiazole, azepine, N-methylazepine, imidazoline, N-methylimidazoline, pyrazine, thiazine, indole, N-methylindole, isoindole, N-methylisoindole, benzimidazole , Purine, N-methylpurine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, carbazole, N-methylcarbazole, 2,6-lutidine, 3,5-lutidine, amidine, guanidine, methyleneamine, acetonitrile, benzonitrile, nicotine And nicotinic acid amide.

  The properties of the non-acidic organic compound are not particularly limited, but those that are solid at room temperature and atmospheric pressure are preferably those that are easily dissolved in a polymerization solvent, and those that are easily liquefied by heating or the like alone. More preferably, it is more preferable that it is liquid alone at room temperature and atmospheric pressure.

  The addition amount of the non-acidic organic compound is preferably 0.01 times mol or more and 10 times mol or less, more preferably 0.1 times mol or more and 7.0 times mol or less with respect to the metal residue, It is more preferable that it is 1.0 times mol or more and 5.0 times mol or less.

(N-oxide compound)
The N-oxide compound is a group of compounds having a functional group represented by N ⁺ —O ⁻ (N = O, N → O as another notation) or N—O. A compound derived by oxidizing a nitrogen-containing compound having a reducing nitrogen atom in the molecule, such as an amine, a tertiary amine, a nitrogen-containing heterocyclic compound, an imine compound, and a nitrile compound. The structure is not particularly limited as long as it is a compound generally referred to as an “N-oxide compound”, but typical structures are those represented by the following formulas (1), (2), (3) and (4). It can be expressed by a formula.

In formula (1), R ₁ , R ₂ , and R ₃ are aliphatic chain substituents having 30 or less carbon atoms, including a substituent composed of an element selected from H, O, N, S, and P , An aromatic cyclic substituent containing an aliphatic cyclic substituent or a heterocyclic ring, or a heteroaliphatic cyclic substituent, and R ₁ , R ₂ , and R ₃ may be the same as or different from each other. R1 and R2 bonded to the N-oxide group are bonded together and bonded to the N atom of the N-oxide group by a double bond, and are composed of elements selected from H, O, N, S, and P It may be an aliphatic chain substituent having 30 or less carbon atoms, an aliphatic cyclic substituent, or a heteroaliphatic cyclic substituent containing a group.

R ₁ , R _2, and R ₃ bonded to the N-oxide group are combined and bonded to the N atom of the N-oxide group through a triple bond, and are selected from H, O, N, S, and P. It may be an aliphatic chain-like substituent having 30 or less carbon atoms including a substituent composed of an element.

  In formula (2), ring A is an aliphatic heterocycle having 3 to 10 ring members or an aromatic heterocycle composed of an element selected from H, C, O, N, and S. B and ring C are aromatic rings, aliphatic rings, heteroaromatic rings, and heteroaliphatic rings having 3 to 10 ring members composed of an element selected from H, C, O, N, and S. Ring A, ring B, and ring C are bonded to each other at an arbitrary position to form a condensed ring. Ring A does not necessarily form a condensed ring with ring B and ring C, and may be a single heteroaromatic ring or heteroaliphatic ring. Further, when ring A forms a condensed ring with ring B, ring C is not necessarily bonded. Ring A may have one or more substituents which are the same or different from each other and are composed of an element selected from H, O, N, S and P.

  Ring B and ring C may have one or more substituents that are the same or different from each other and are composed of an element selected from H, O, N, S, and P. Further, each of the ring B and the ring C may have a different ring structure or the same ring structure. Ring B and Ring C are positions different from the position bonded to Ring A, and are independently an aromatic ring, an aliphatic ring, a hetero ring composed of an element selected from H, O, N, S, and P. An aromatic ring or a heteroaliphatic ring may form a condensed ring.

In the formula, R ₄ includes an aliphatic chain substituent having 30 or less carbon atoms, an aliphatic cyclic substituent or a heterocyclic ring containing a substituent composed of an element selected from H, O, N, S, and P. It is an aromatic attribute cyclic substituent or heteroaliphatic cyclic substituent, and the valence of the N atom of the N-oxide group satisfies tetravalence only by the atoms constituting the ring A and the O atom of the N-oxide group. If you do not need to join.

In the formula (3), R ₅ and R ₆ are aliphatic chain-like substituents having 30 or less carbon atoms, including a substituent composed of an element selected from H, O, N, S, and P, and aliphatic cyclic It is an aromatic attribute cyclic substituent containing a substituent or a heterocycle, or a heteroaliphatic cyclic substituent, and R ₅ and R ₆ may be the same or different from each other.

  In formula (4), ring D is an aliphatic heterocycle having 3 to 10 ring members and composed of an element selected from H, C, O, N, and S, and ring E and ring F are An aromatic ring, an aliphatic ring, a heteroaromatic ring, and a heteroaliphatic ring having 3 to 10 ring members composed of an element selected from H, C, O, N, and S. Ring D, ring E, and ring F are bonded to each other at an arbitrary position to form a fused ring. Ring A does not necessarily form a condensed ring with ring B and ring C, and may be a single heteroaliphatic ring. Moreover, when the ring D forms a condensed ring with the ring E, the ring F does not necessarily need to couple | bond together. Ring D may have one or more substituents which are the same or different from each other and are composed of an element selected from H, O, N, S and P.

  Ring E and ring F may have one or more substituents which are the same or different from each other and are composed of an element selected from H, O, N, S and P. Further, each of the ring E and the ring F may have a different ring structure, or may have the same ring structure. Ring E and Ring F are positions different from the position bonded to Ring D, and are independently an aromatic ring, an aliphatic ring, a hetero ring composed of an element selected from H, O, N, S, and P. An aromatic ring or a heteroaliphatic ring may form a condensed ring.

  The N-oxide compound is not particularly limited, but the N-oxide compound may have any structure obtained by oxidizing the nitrogen-containing compound group shown below with an oxidizing agent such as hydrogen peroxide, persulfuric acid, or metachloroperbenzoic acid. It may be a compound having a functional group other than the structure, may have two or more N-oxide structures in the molecule, and may be a hydrate. Examples of nitrogen-containing compounds having a parent structure of an N-oxide compound include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, ethylenediamine, hexamethylenediamine, hexamethyleneimine, N-methylhexamethyleneimine, triethylamine, N-cyclohexyl Amine, N, N-cyclohexylmethylamine, N, N-dimethyldodecylamine, aniline, N, N-dimethylaniline, piperidine, N-methylpiperidine, piperidone, N-methylpiperidone, piperazine, N-methylpiperidine, morpholine, N -Methylmorpholine, 2,2,6,6-tetramethyl N-methylmorpholine, 2,2,6,6-tetramethyl-1-piperidine, 8-azabicyclo [3.2.1] octane, 7-azabicyclo [ 2.2. ] Heptane, 2-azaadamantane, 1-methyl-2-azaadamantane, pyrrole, N-methylpyrrole, pyridine, α-picoline, pyridazine, pyrimidine, 1,3,5-triazine, imidazole, N-methylimidazole, pyrazole N-methylpyrazole, oxazole, thiazole, azepine, N-methylazepine, imidazoline, N-methylimidazoline, pyrazine, thiazine, indole, N-methylindole, isoindole, N-methylisoindole, benzimidazole, purine, N -Methylpurine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, carbazole, N-methylcarbazole, 2,6-lutidine, 3,5-lutidine, amidine, guanidine, methyleneamine, acetonitrile Benzonitrile, nicotine, nicotinic acid, and nicotinic acid amide.

  Specific N-oxide compounds are not particularly limited as long as they are generally used, but 3-acetylpyridine N-oxide, 2-aminopyridine N-oxide, pyridine N-oxide, 4-chloro Pyridine N-oxide, 4-cyanopyridine N-oxide, 4- (dimethylamino) viridine N-oxide hydrate, 8-aminoquinoline N-oxide, 2-bromo-4-nitropyridine N-oxide, N-tert -Butyl-α-phenylnitrone, N-tert-butyl-α- (4-pyridyl-1-oxide) nitrone, 5,5-dimethyl-1-pyrroline N-oxide, quinoline N-oxide, 4- (hydroxyamino) ) Quinoline N-oxide, 2-hydroxypyridine N-oxide, 3-hydroxypyridine N-oxide, isonico Stannic acid N-oxide, isoquinoline N-oxide, 2,6-lutidine N-oxide, 3,5-lutidine N-oxide, 2-mercaptopyridine N-oxide, 2-mercaptopyridine N-oxide sodium, 4-methoxypyridine N-oxide, 4-methylmorpholine N-oxide, N-methylmorpholine N-oxide 2-methylpyridine N-oxide, 3-methylpyridine N-oxide, 4-methylpyridine N-oxide, nicotinamide N-oxide, nicotine Acid N-oxide, 4-nitropyridine N-oxide, 4-nitropyridine N-oxide, 4-phenylpyridine N-oxide, scopolamine N-oxide hydrobromide, 3,3,5,5-tetramethyl- 1-pyrroline N-oxide, trimethylamine N-oxide, 2,2, , 6-tetramethyl-1-piperidine N-oxyl, [8-azabicyclo [3.2.1] octane N-oxyl], [7-azabicyclo [2.2.1] heptane N-oxyl], 2-aza Examples include adamantane N-oxyl, 1-methyl-2-azaadamantane N-oxyl, triethylamine N-oxide, tripropylamine N-oxide, and dimethylethylamine N-oxide. Further, an N-oxide type surfactant having an N-oxide structure in the molecule such as n-dodecyl-dimethylamine-N-oxide can also be used effectively.

  In the present embodiment, the order of adding the non-acidic organic compound and the N-oxide compound to the polymer solution is not particularly limited, but after adding the non-acidic organic compound, the N-oxide compound may be added, The N-oxide compound may be dissolved in a liquid non-acidic organic compound and added to the polymer solution.

  In step 2, the molar ratio of N-oxide to metal residue is preferably 0.01 or more and 10 or less, more preferably 0.1 or more and 7.0 or less, and 1.0 or more and 5.0 or less. More preferably. In particular, when the metal residue is lithium and titanium, the molar ratio is more preferably in the above range.

  When N-oxide is added as an aqueous solution to the polymer solution, the amount of water mixed with N-oxide is preferably 0.1 volume times or more and 20 volume times or less with respect to the polymer solution, More preferably, it is 0.2 volume times or more and 10 volume times or less, and 0.5 volume times or more and 5.0 volume times or less. When the amount of water added is within the above range, metal residues contained in the polymer solution are easily removed, and the amount of waste water tends to be reduced.

[Step 3]
In step 3, the polymer solution obtained in step 2 is mixed with an acid. Here, the acid may be an organic acid or an inorganic acid, and the pH of the aqueous solution when the acid compound and water are mixed to form an aqueous solution is 1 or more and less than 7. The organic acid is an organic compound having one or more acidic functional groups selected from a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group in the molecule alone or in combination. In addition, when the aqueous solution is used, the pH is less than 4 and it is expected that an excessive burden is imposed on the production equipment. If the pH is less than 7 in advance with a basic salt of an alkali metal or alkaline earth metal, It may be a mixture of four or more organic acids and organic acid salts.

  In this embodiment, the structure of the organic acid compound is not particularly limited, and generally known organic acids can be used. Specific examples of organic acids include oxalic acid, citric acid, maleic acid, malic acid, malonic acid, lactic acid, gluconic acid, tartaric acid, glutaric acid, ascorbic acid, formic acid, acetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Examples include glycine, alanine, cystine, serine, inositol trisphosphate, phytic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid.

  Moreover, although an inorganic acid is not specifically limited, Hydrochloric acid, a sulfuric acid, phosphoric acid, nitric acid is mentioned.

  In step 3, the molar ratio of acid to lithium and / or titanium is preferably 0.1 or more and 50 or less, more preferably 0.25 or more and 20 or less, and further preferably 0.5 or more and 10 or less. By using an acid within the above range, lithium and titanium can be effectively removed, and the residual acid compound in the polymer can be reduced.

  The addition of the acid compound is not particularly limited, such as preparing an aqueous solution of the acid compound in advance and mixing it with the polymer solution, or adding the acid compound after mixing the polymer solution and water, From the viewpoint of simplification of the process, it is preferable to add an aqueous solution of an acid compound to the polymer solution. In this case, the concentration of the aqueous solution of the acid compound is not particularly limited, but the total amount of the aqueous phase after mixing the polymer solution, water, and the aqueous acid compound solution is 0.1 volume times or more and 20 volume times the polymer solution. It is preferable to adjust so that it may become the following ranges.

[Step 4]
In the step 3, the mode of mixing the polymer solution, the N-oxide compound, and the acid aqueous solution is not particularly limited. For example, the meshing as described in FIG. 1 (cited from JP-A-6-136634) is used. It is preferable to use a rotary disperser having a structure from the viewpoint of improving the metal removal rate and shortening the time required for the deashing operation. The meshing structure of the rotary disperser is a structure in which a rotor having a shape of comb teeth or holes is meshed with a stator. The mixture of the polymerization solution and the aqueous solution charged in the rotary disperser receives centrifugal force when the rotor rotates at high speed, and flows to the discharge port through the gap between the rotor and the stator. During this time, a shearing force acts in a minute gap between the rotor and the stator, and the structure is uniformly dispersed.

In the operation of the rotary disperser, the P / V value is set to 3 × 10 ⁴ (kw / m ³ ) or more, preferably 5 × 10 ⁴ (kw / m ³ ), more preferably 1 × 10 ⁵ (kw / m). By setting m ³ ), strong shear can be given. Here, P (kw) is the power of the rotary disperser and can be easily obtained by measuring the power consumption during mixing. V (m ³ ) is the space volume of the mixing part in the rotary disperser, and is the space volume of the part that gives a shearing force to the solution. Further, the peripheral speed (2πr · n) is 5 (m / s) or more, preferably 7 (m / s), more preferably 10 (m / s). Here, r (m) is the radius of the outermost tooth of the rotor in the rotary disperser, and n (s ⁻¹ ) is the rotational speed of the rotor in the rotary disperser. By operating the rotary disperser under the above conditions, the polymer solution and water, the acid compound, and the organic acid can be mixed efficiently, and a good metal with a short average residence time of 0.01 to 10 (s) The removal efficiency tends to be obtained.

[Step 5]
Step 5 is a step of obtaining a polymer by further removing the solvent from the polymer solution purified by removing (separating) the aqueous phase from the mixed solution. The method for separating water in step 5 is not particularly limited as long as it is generally used in the art. For example, the mixed solution composed of the polymer solution and the aqueous layer is subjected to stationary separation, centrifugation, and countercurrent flow. A method of removing the aqueous phase by extraction or the like can be mentioned. The solvent removal treatment is not particularly limited as long as it is generally used. For example, a method of obtaining a polymer crumb by steam stripping, direct removal by a drum dryer or a devolatilizing extruder. Examples thereof include a method for obtaining a polymer by treatment.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

[Production Example 1]
400 g of polystyrene-polybutadiene-polystyrene block copolymer (styrene content: 30.0% by mass, butadiene content: 70.0% by mass, weight average molecular weight: 50,000) produced by anionic polymerization using n-BuLi as a catalyst. 2800 g of the cyclohexane solution contained was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Thereafter, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride are added, and a hydrogenated polymer solution is obtained by pressurizing with 10 kg / cm ² of hydrogen to perform a hydrogenation reaction. Got. As a result of analyzing the hydrogenated polymer (polymer) by NMR, it was confirmed that 98% or more of the double bonds in the polybutadiene block were hydrogenated. The amount of metal contained in the obtained polymer was measured through elemental analysis using inductively coupled plasma (ICP), and as a result, Ti residue: 102 ppm, Li residue: 100 ppm, Al residue: 101 ppm. It was.

[Production Example 2]
400 g of polystyrene-polybutadiene-polystyrene block copolymer (styrene content: 30.0% by mass, butadiene content: 70.0% by mass, weight average molecular weight: 50,000) produced by anionic polymerization using n-BuLi as a catalyst. 2800 g of the cyclohexane solution contained was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Thereafter, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride are added, and a hydrogenated polymer solution is obtained by pressurizing with 10 kg / cm ² of hydrogen to perform a hydrogenation reaction. Got. As a result of analyzing the hydrogenated polymer (polymer) by NMR, it was confirmed that 80% of the double bonds in the polybutadiene block were hydrogenated. The amount of metal contained in the obtained polymer was measured through elemental analysis using inductively coupled plasma (ICP), and as a result, Ti residue: 100 ppm, Li residue: 102 ppm, Al residue: 100 ppm. It was.

[Production Example 3]
400 g of polystyrene-polybutadiene-polystyrene block copolymer (styrene content: 30.0% by mass, butadiene content: 70.0% by mass, weight average molecular weight: 50,000) produced by anionic polymerization using n-BuLi as a catalyst. 2800 g of the cyclohexane solution contained was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Thereafter, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride are added, and a hydrogenated polymer solution is obtained by pressurizing with 10 kg / cm ² of hydrogen to perform a hydrogenation reaction. Got. As a result of analyzing the hydrogenated polymer (polymer) by NMR, it was confirmed that 30% of the double bonds in the polybutadiene block were hydrogenated. The amount of metal contained in the obtained polymer was measured through elemental analysis using inductively coupled plasma (ICP), and as a result, Ti residue: 103 ppm, Li residue: 100 ppm, Al residue: 101 ppm. It was.

[Production Example 4]
2800 g of a cyclohexane solution containing 400 g of a polybutadiene polymer (butadiene content: 100.0 mass%, weight average molecular weight: 200,000) produced by anionic polymerization using n-BuLi as a catalyst was placed in a 5 liter autoclave reactor at 400 rpm. And heated to 60 ° C. with stirring. Thereafter, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride are added, and a hydrogenated polymer solution is obtained by pressurizing with 10 kg / cm ² of hydrogen to perform a hydrogenation reaction. Got. As a result of analyzing the hydrogenated polymer (polymer) by NMR, it was confirmed that 80% of the double bonds in the polybutadiene block were hydrogenated. The amount of metal contained in the obtained polymer was measured through elemental analysis using inductively coupled plasma (ICP), and as a result, Ti residue: 102 ppm, Li residue: 101 ppm, Al residue: 102 ppm. It was.

[Production Example 5]
2800 g of a cyclohexane solution containing 400 g of a polybutadiene polymer (butadiene content: 100.0 mass%, weight average molecular weight: 200,000) produced by anionic polymerization using n-BuLi as a catalyst was placed in a 5 liter autoclave reactor at 400 rpm. And heated to 60 ° C. with stirring. Thereafter, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride are added, and a hydrogenated polymer solution is obtained by pressurizing with 10 kg / cm ² of hydrogen to perform a hydrogenation reaction. Got. As a result of analyzing the hydrogenated polymer (polymer) by NMR, it was confirmed that 30% of the double bonds in the polybutadiene block were hydrogenated. The amount of metal contained in the obtained polymer was measured through elemental analysis using inductively coupled plasma (ICP), and as a result, Ti residue: 100 ppm, Li residue: 102 ppm, Al residue: 100 ppm. It was.

[Production Example 6]
400 g of polystyrene-polybutadiene-polystyrene block copolymer (styrene content: 30.0% by mass, butadiene content: 70.0% by mass, weight average molecular weight: 100,000) produced by anionic polymerization using n-BuLi as a catalyst. 2800 g of the cyclohexane solution contained was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Thereafter, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride are added, and a hydrogenated polymer solution is obtained by pressurizing with 10 kg / cm ² of hydrogen to perform a hydrogenation reaction. Got. As a result of analyzing the hydrogenated polymer (polymer) by NMR, it was confirmed that 80% of the double bonds in the polybutadiene block were hydrogenated. The amount of metal contained in the obtained polymer was measured through elemental analysis using inductively coupled plasma (ICP), and as a result, Ti residue: 102 ppm, Li residue: 100 ppm, Al residue: 104 ppm. It was.

[Method for measuring physical properties of hydrogenated conjugated diene polymer obtained in Examples and Comparative Examples]
Measurement of metal compound in terms of metal atom (metal content) contained in hydrogenated conjugated diene polymers obtained in Examples or Comparative Examples Hydrogenated conjugated diene polymers obtained in Examples or Comparative Examples described later The amount of metal contained therein was measured using inductively coupled plasma (ICP, Inductive Coupled Plasma, manufactured by Shimadzu Corporation, apparatus name: ICPS-7510). First, the polymer is completely dissolved in sulfuric acid and nitric acid, an aqueous solution containing metal components is sprayed into argon plasma, the intensity of the wavelengths of light unique to the various metal elements emitted from it is measured, and a calibration curve method is used. The amount of metal contained in the hydrogenated conjugated diene polymer was determined. Specifically, the metal amounts of Li, Ti, and Al were determined.

[Insoluble gel component amount (number of visible gels, filtration time]
A Buchner funnel equipped with 5A filter paper (for JIS P 3801 chemical analysis) was attached to a suction bottle with an internal volume of 2000 mL, and the pressure in the suction bottle was reduced to 35 kPa using a vacuum pump. Using this filtration device, a solution in which 15 g of polymer was dissolved in 600 ml of toluene was subjected to suction filtration, and the time from the start of filtration until the liquid level gradually decreased and the surface of the filter paper was exposed from the liquid level was measured. It was measured. Further, after complete filtration, the filter paper was dried, and the insoluble gel component remaining on the filter paper was stained with a staining solution. The number of insoluble gel components having a diameter of 1 mm or more was measured using a digital microscope (VHX-6000 manufactured by Keyence).

[Color tone]
A hydrogenated conjugated diene polymer obtained in Examples and Comparative Examples described later is compression-molded to prepare a sheet having a thickness of 2 mm, and the b value of the obtained sheet is measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.). ZE-2000). It was evaluated that the hydrogenated conjugated diene polymer molded body had a strong yellowish color and a poor color tone as the b value increased.
[Evaluation criteria]
AAA: b value is less than 2 AA: b value is 2 or more and less than 3 A: b value is 3 or more and less than 5 B: b value is 5 or more and less than 10 C: b value is 10 or more

[Example 1]
To the polymer solution obtained in Production Example 1, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and 2-fold mol malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in 2 volumes of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 2]
To the polymer solution obtained in Production Example 1, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and 2-fold mol of citric acid was polymerized with respect to the metal residue. An aqueous solution dissolved in 2 volumes of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes with a mixer equipped with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 3]
To the polymer solution obtained in Production Example 1, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and then 2-fold mol of aqueous sulfuric acid solution was doubled with respect to the metal residue. The diluted aqueous solution was added to a volume of water and vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 4]
To the polymer solution obtained in Production Example 1, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and 2-fold mol malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in double volume of water is added to the solution, and mixed for 1 second (sec) under conditions of 60 ° C. and 7600 rpm by a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko). A mixture was obtained. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 5]
To the polymer solution obtained in Production Example 1, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and 2-fold mol of citric acid was polymerized with respect to the metal residue. An aqueous solution dissolved in double volume of water is added to the solution, and mixed for 1 second (sec) under conditions of 60 ° C. and 7600 rpm by a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko). A mixture was obtained. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 6]
To the polymer solution obtained in Production Example 1, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and then 2-fold mol of aqueous sulfuric acid solution was doubled with respect to the metal residue. A dilute aqueous solution was added to a volume of water, and the mixture was mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.) to obtain a mixed solution. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 7]
To the polymer solution obtained in Production Example 2, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and the 2-fold mol malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in 2 volumes of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes with a mixer equipped with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.
[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 8]
To the polymer solution obtained in Production Example 3, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and 2-fold mol citric acid was polymerized with respect to the metal residue. An aqueous solution dissolved in 2 volumes of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes with a mixer equipped with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 9]
To the polymer solution obtained in Production Example 2, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and the 2-fold mol malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in double volume of water is added to the solution, and mixed for 1 second (sec) under conditions of 60 ° C. and 7600 rpm by a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko). A mixture was obtained. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 10]
To the polymer solution obtained in Production Example 3, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and 2-fold mol of malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in double volume of water is added to the solution, and mixed for 1 second (sec) under conditions of 60 ° C. and 7600 rpm by a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko). A mixture was obtained. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 11]
To the polymer solution obtained in Production Example 2, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and then 2-fold mol sulfuric acid aqueous solution was doubled with respect to the metal residue. The diluted aqueous solution was added to a volume of water and vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 12]
To the polymer solution obtained in Production Example 3, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and then 2-fold mol of sulfuric acid aqueous solution was doubled with respect to the metal residue. The diluted aqueous solution was added to a volume of water and vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 13]
To the polymer solution obtained in Production Example 2, N-pyridine oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and then 2-fold mol sulfuric acid aqueous solution was doubled with respect to the metal residue. A dilute aqueous solution was added to a volume of water, and the mixture was mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.) to obtain a mixed solution. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 14]
To the polymer solution obtained in Production Example 3, n-dodecyl-dimethylamine-N-oxide dissolved in 2-fold mol ethanol with respect to the metal residue was added, and then 2-fold mol with respect to the metal residue. An aqueous solution obtained by diluting an aqueous sulfuric acid solution in 2 volumes of water is added, and mixed by mixing for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser having a meshing structure (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.). A liquid was obtained. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 15]
To the polymer solution obtained in Production Example 4, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and then 2-fold mol of malic acid aqueous solution was added to the metal residue. An aqueous solution diluted in double volume of water was added and mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure to obtain a mixed solution. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 16]
To the polymer solution obtained in Production Example 5, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and then 2-fold mol of malic acid aqueous solution was added to the metal residue. An aqueous solution diluted in double volume of water was added and mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure to obtain a mixed solution. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Example 17]
To the polymer solution obtained in Production Example 6, N-pyridine oxide dissolved in 2-fold mol of ethanol with respect to the metal residue was added, and then 2-fold mol of malic acid aqueous solution was added to the metal residue. An aqueous solution diluted in double volume of water was added and mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure to obtain a mixed solution. The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Comparative Example 1]
60% of the polymer solution obtained in Production Example 1, 30% hydrogen peroxide solution twice the volume of the polymer solution, and 2 times mol of malic acid with respect to titanium were mixed in a mixer equipped with a stirrer. Stir vigorously at 10 ° C. for 10 minutes. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP). The measurement results are shown in Table 1.

[Comparative Example 2]
60% of the polymer solution obtained in Production Example 2, 30% hydrogen peroxide solution twice the volume of the polymer solution, and 2 times mol of malic acid with respect to titanium were mixed in a mixer equipped with a stirrer. Stir vigorously at 10 ° C. for 10 minutes. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP). The measurement results are shown in Table 1.

[Comparative Example 3]
The polymer solution obtained in Production Example 3, 30% hydrogen peroxide solution twice the volume of the polymer solution, and 2 times moles of malic acid with respect to titanium were mixed in a mixer equipped with a stirrer. Stir vigorously at 10 ° C. for 10 minutes. Thereafter, the obtained mixed liquid was retained for 5 minutes to separate the polymer solution phase and the aqueous phase. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP). The measurement results are shown in Table 1.

[Comparative Example 4]
To the polymer solution obtained in Production Example 1, an aqueous solution in which 2-fold mol of malic acid is dissolved in 2-fold volume of water with respect to the metal residue is added to the metal residue, thereby having a meshing structure. The mixture was obtained by mixing for 1 second (sec) under the conditions of 60 ° C. and 7600 rpm using a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.). The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Comparative Example 5]
To the polymer solution obtained in Production Example 2, an aqueous solution in which 2-fold mol of malic acid is dissolved in 2-fold volume of water with respect to the metal residue is added to the metal residue, thereby having an interlocking structure. The mixture was obtained by mixing for 1 second (sec) under the conditions of 60 ° C. and 7600 rpm using a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.). The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Comparative Example 6]
The polymer solution obtained in Production Example 3 is added with an aqueous solution in which 2-fold mol of malic acid is dissolved in 2-fold volume of water with respect to the metal residue, and has a meshing structure. The mixture was obtained by mixing for 1 second (sec) under the conditions of 60 ° C. and 7600 rpm using a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.). The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

[Comparative Example 7]
To the polymer solution obtained in Production Example 6, an aqueous solution in which 2-fold moles of malic acid is dissolved in 2-fold volume of water with respect to the metal residue is added to the metal residue to have a meshing structure. The mixture was obtained by mixing for 1 second (sec) under the conditions of 60 ° C. and 7600 rpm using a rotary disperser (Cabitron 1010 manufactured by Nikko Kogyo Co., Ltd.). The P / V value at this time was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained liquid mixture was sent to the tank heated at 60 degreeC, and was retained for 5 minutes, and the polymer solution phase and the water phase were isolate | separated. The separation state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Metal content measurement]
The amount of metal contained in the obtained solid polymer was measured through elemental analysis using inductively coupled plasma (ICP).

Claims (7)

A conjugated diene polymer containing a conjugated diene compound unit, or a conjugated diene block polymer containing a polymer block containing a conjugated diene compound unit,
The metal content in the polymer having a weight average molecular weight of 10,000 or more and 1,000,000 or less is 0.10 mass ppm or more and 30 mass ppm or less,
The content of the insoluble gel component satisfies the following conditions:
Polymer:
(Content of insoluble gel component)
The polymer solution dissolved in the organic solvent is filtered off with a filter paper, and the number of visible gels visible on the filter paper is 2 or less. The polymer is the conjugated diene block polymer,
The conjugated diene block polymer further contains a polymer block containing a vinyl aromatic hydrocarbon unit.
The polymer according to claim 1. The total hydrogenation rate H of double bonds derived from the conjugated diene compound is 5.0% or more and 100% or less,
The polymer according to claim 1 or 2. The metal is one or more organic salts or inorganic salts selected from the group consisting of titanium metals, lithium metals, aluminum metals, and nickel metals,
The polymer according to any one of claims 1 to 3. A polymer containing a polymer containing a conjugated diene compound unit or a polymer block containing a conjugated diene compound unit, wherein the polymer has a weight average molecular weight of 10,000 to 1,000,000. , A method for producing a polymer that is 0.10 mass ppm or more and 30 mass ppm or less,
Having the following steps 1-5,
A method for producing a polymer.
Step 1: Step of preparing a polymer solution containing water and / or an organic solvent and lithium and / or titanium Step 2: Step of bringing the polymer solution into contact with an N-oxide compound Step 3: Step of the polymer solution and acid Step 4: Step of mixing the polymer solution Step 5: Step of removing water and / or organic solvent from the polymer solution In step 2, the molar ratio of the N-oxide compound to the lithium and / or titanium is 0.01 or more and 10 or less.
The manufacturing method of the polymer of Claim 5. In step 3, the molar ratio of the acid to the lithium and / or titanium is 0.1 or more and 50 or less.
The manufacturing method of the polymer of Claim 5 or 6.