JP6885766B2 - Polymer and its production method - Google Patents

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 and which do not require a vulcanization step and can be molded and recycled like thermoplastic resins have been 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 that is copolymerizable with the conjugated diene monomer and the conjugated diene monomer. The copolymer with is very important as an impact-resistant transparent resin or a modifier for polyolefin and polystyrene resins.

Further, the hydrogenated polymer in which hydrogen is added to the olefinic double bond portion contained in the conjugated diene polymer has a feature of being excellent in weather resistance. Taking advantage of this feature, hydrogenated polymers are used in automobile parts, home appliance parts, electric wire coatings, medical parts, miscellaneous goods, footwear, and the like.

Generally, the conjugated diene-based polymer is produced by living anionic polymerization using an alkyllithium or the like as an initiator. Further, when a hydrogenated polymer is obtained, after the polymerization, a hydrogenation reaction (hereinafter, also referred to as “hydrogenation reaction”) is carried out on the olefinic double bond portion using a metal of Group VIII or Group IV of the periodic table as a catalyst. Do.

Various methods have been reported for hydrogenating a polymer having an olefinic double bond, for example, appropriate reduction of a Group VIII metal of the Periodic Table, particularly a compound of nickel or cobalt and an alkylaluminum compound. A method of hydrogenation using a catalyst in which an agent is combined is known. In addition, a catalyst in which a compound of titanium which is a metal of Group IV of the periodic table, for example, a bis (cyclopentadienyl) titanium compound and an appropriate reducing agent such as an alkylaluminum compound is combined is used, and a conjugated diene-based weight is used. A method of hydrogenating an unsaturated double bond of coalescence is known.

In a hydrogenation reaction using a homogeneous catalyst, a high hydrogenation rate and high reproducibility can generally be obtained 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 components remaining in the polymer react with air, ultraviolet rays, etc. to cause oxidative decomposition of the polymer and deterioration of the hue of the product, which causes a significant decrease in commercial value. Therefore, they are removed by decalcification operation. Is desirable. In general, homogeneous catalysts are difficult to physically decalcify by filtration or the like after the reaction, and water solubility is increased by a chemical reaction, and separation by washing with water or the like is required.

Therefore, for the purpose of solving this problem, some proposals have been made as a decalcification method for metal species remaining in the polymer solution.

For example, regarding the removal of a metal catalyst of Periodic Table VIII such as nickel, Patent Document 1 discloses a method of treating with an oxidizing agent and a dicarboxylic acid in order to remove a residue, and Patent Document 2 discloses an oxidized metal as a silicate. A method of adsorbing on a silicate to remove a catalyst is disclosed. Further, Patent Document 3 discloses a method of removing a nickel catalyst that has reacted with oxygen by adsorbing it on activated carbon. As for the method of removing the titanium residue, Patent Document 4 describes a method of oxidizing a metal species with excess hydrogen peroxide and washing with a polyvalent carboxylic acid aqueous solution, or a method of adding a polyvalent carboxylic acid aqueous solution and chewing. A method for efficiently removing most of the metals by highly mixing using a rotary disperser having a laminated structure is disclosed.

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

However, conjugated diene polymers produced using these methods are gelled and heavy because a part of the polymer structure is uniformly oxidized by an oxidizing agent to form a crosslinked structure between the polymers. There is a problem in diffusing as an insoluble component in the coalesced solution. Usually, these insoluble components are filtered by a filter such as a strainer and treated so as not to be mixed in the product. However, since the insoluble component often clogs the filter, it is essential to clean the filter several times a day, and the loss of the gelled polymer deteriorates the production yield. Further, for the partially hydrogenated conjugated diene polymer, since many double bond portions having high reactivity to the oxidation reaction remain, the decalcification operation using the above-mentioned oxidizing agent cannot be performed.

For this reason, partially hydrogenated conjugated diene polymers with low metal residues have not been industrially produced so far.

Further, the technique described in Patent Document 4 describes a method for reducing metal residues from the product. That is, a method for reducing metal residues in a product by using organic acidic water is described. 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 high molecular weight polymer and condenses and solidifies, and the interface between the organic phase and the aqueous phase is equivalent to the gel content. There is a problem that insoluble components are generated over time. Since this insoluble component is generated after the rubber solution has passed 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 a metal component. It becomes a factor to make it. In addition, it is stated that the efficiency of decalcification can be improved by using hydrogen peroxide or the like, but since a large excess of an oxidizing agent having strong oxidizing power is used, aging added in the finishing process. There is a problem that the color is colored by oxidizing the inhibitor and the color tone of the product is impaired, and there is a problem that an excessive burden is applied to the manufacturing equipment. Further, as described above, hydrogen peroxide oxidatively crosslinks the residual double bonds in the polymer molecule as an oxidizing agent, so that the generation of the gel component cannot be suppressed.

Therefore, there is a strong demand for a hydrogenated conjugated diene polymer having an extremely small amount of gel content in the production process and the product, a small amount of metal residue remaining in the product, and an excellent color tone, and a method for producing the same. ..

Therefore, the present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a polymer in which the amount of residual metal residue is extremely small and the amount of residual insoluble gel component is extremely small. To do.

As a result of diligent studies to solve the above problems, the present inventor has a conjugated diene-based polymer containing a conjugated diene compound unit or a conjugated diene-based block weight containing a polymer block containing a conjugated diene compound unit. When the metal content in the polymer which is a coalescence and has a weight average molecular weight of 10,000 or more and 1 million or less is within a predetermined range, the amount of residual metal residue is extremely small, and the remaining insoluble gel component is extremely small. I found that there are few.

Further, by using a production method having a predetermined step, the generation of the insoluble gel component is controlled to an extremely small amount, the metal species are efficiently removed from the polymer solution, the metal content is extremely low, and the insoluble gel component is removed. We have found that a conjugated diene-based polymer containing almost no amount can be produced, and have completed the present invention.

That is, the present invention is as follows.
[1]
A conjugated diene-based polymer containing a conjugated diene compound unit, or a conjugated diene-based 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 million 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 solution of the polymer dissolved in the organic solvent is suction-filtered using 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-based block polymer.
The conjugated diene-based 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 the double bond 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 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 conjugated diene compound unit or a polymer containing a polymer block containing a conjugated diene compound unit, wherein the metal content in the polymer having a weight average molecular weight of 10,000 or more and 1 million or less is , 0.10 mass ppm or more and 30 mass ppm or less, which is a method for producing a polymer.
It has the following steps 1-5.
Method for producing polymer.
Step 1: Prepare a polymer solution containing water and / or an organic solvent and lithium and / or titanium Step 2: Contact the polymer solution with the N-oxide compound Step 3: The polymer solution and acid Step 4: Mixing the polymer solution Step 5: Removing water and / or organic solvent from the polymer solution [6]
In step 2, the molar ratio of the N-oxide compound to lithium and / or titanium is 0.01 or more and 10 or less.
The method for producing a polymer according to [5].
[7]
In step 3, the molar ratio of the acid to lithium and / or titanium is 0.1 or more and 50 or less.
The method for producing a polymer according to [5] or [6].

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

(A) is a side sectional view for explaining an example of the rotary disperser used in the present invention. 1 is a rotor and 2 is a stator. Further, (B) shows the engagement of 1 and 2 in the view 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 can be variously modified and implemented within the scope of the gist thereof.

[Polymer]
The polymer of the present embodiment is a conjugated diene-based polymer containing a conjugated diene compound unit, or a conjugated diene-based 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 or more and 1 million or less is 0.10 mass ppm or more and 30 mass ppm or less. Further, in the polymer of the present embodiment, the content of the insoluble gel component satisfies the following conditions.
(Content of insoluble gel component)
The solution of the polymer dissolved in the organic solvent is suction-filtered using a filter paper, and the number of visible gels visible on the filter paper is 2 or less.

<Conjugated diene polymer>
The conjugated diene-based polymer of the present 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.

The conjugated diene compound is not particularly limited, and examples thereof include an aliphatic conjugated diene compound, for example, 1,3-butadiene, isoprene, piperylene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4, Examples thereof include conjugated diene compounds containing 4 to 12 carbon atoms such as 5-diene-1,3-octadien. Of these, 1,3-butadiene and isoprene are preferable. The conjugated diene-based polymer is a homopolymer obtained by polymerizing one of these conjugated diene compounds, or a copolymer obtained by polymerizing two or more of these conjugated diene compounds.

The homopolymer of the conjugated diene compound is a polymer mainly composed of the conjugated diene compound, but when the conjugated diene-based copolymer contains a compound other than the conjugated diene compound unit as a monomer unit, "conjugated diene-based polymer". The term "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-based block polymer of the present embodiment has a content of one or more conjugated diene compound units of 5.0% by mass or more and 95% by mass or less, and is generally called a block copolymer. The structure is not particularly limited. A conjugated diene-based block polymer contains one or more conjugated diene compound units forming one or more polymer block structures in a conjugated diene copolymer in terms of weight average molecular weight. Alternatively, one monomer unit derived from a compound copolymerizable with one or more kinds of conjugated diene compounds has a polymer block structure of 2,000 or more in terms of weight average molecular weight in the conjugated diene-based copolymer. It is preferable that it is formed and contained as described above.

When either or both of the above polymer block structures are contained in a conjugated diene-based block polymer in combination with two or more polymer block structures, the weight average molecular weight of each polymer block is the same. May be different.

When one or more of the above polymer block structures are contained in the conjugated diene copolymer, a block polymer of one or more conjugated diene compounds and a block polymer of a monomer copolymerizable with one or more conjugated diene compounds. Can be a structure in which is linked in an arbitrary sequence, and either a block polymer of one or more conjugated diene compounds, a block polymer of a compound copolymerizable with one or more conjugated diene compounds, or both. However, the structure may be such that the conjugated diene compound is linked by a random copolymer of the conjugated diene compound and a copolymerizable 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.

The polymer obtained by copolymerizing the conjugated diene compound with 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, and is, for example, styrene, α-methylstyrene, styrene substituted with an alkoxy group; 2-vinylpyridine, 4-vinylpyridine, vinylnaphthalene, vinyl substituted with an alkyl group. Examples thereof include vinylallyl compounds such as naphthalene. Of these, styrene and α-methylstyrene are preferable.

More specifically, the following structure can be mentioned as a preferable polymer block structure.
-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 its block weight. A structure in which two block polymers of vinyl aromatic compounds are linked to both ends of the coalescence. ・ A block polymer of an arbitrary number of aliphatic conjugated diene compounds and an arbitrary number of vinyl aromatic compounds A structure in which the block polymer is linked in an arbitrary sequence and both ends are block polymers of a vinyl aromatic compound. A block polymer of one aliphatic conjugated diene compound and an aliphatic compound. A structure in which two random copolymers of a system-conjugated diene compound and a vinyl aromatic compound are linked, and both ends are random copolymers. A block weight of one aliphatic conjugated diene compound. The structure is such that the coalescence, 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, and one end is random. A structure that is a copolymer and is a block polymer of a vinyl aromatic compound at one end.

The content of the vinyl aromatic compound in the conjugated diene polymer or the conjugated diene block polymer is not particularly limited, but is 0% by mass or more and 50% by mass or less, and sufficient performance as a copolymer can be 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 when polymerized from one kind of conjugated diene compound, it may be a homopolymer, and two or more kinds of conjugated diene compound units or one or more kinds of conjugated diene compound units. It may be a random copolymer composed of a vinyl aromatic compound unit and a polymer containing a polymer block mainly composed of a conjugated diene compound (the conjugated diene compound unit is 5.0% by mass or more and 95% by mass or less). Content rate).

The polymer contains at least a polymer having a weight average molecular weight of 10,000 or more and 1 million or less. 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-based block polymer include 1,3-butadiene, isoprene, piperylene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadien. By copolymerization of such a conjugated diene compound containing 4 to 12 carbon atoms, more preferably 1,3-butadiene, isoprene, and a vinyl aromatic compound capable of copolymerizing with any of these. It is a obtained polymer, in which each monomer has the same component and contains a homopolymer block in the copolymer.

When the conjugated diene polymer or the conjugated diene block polymer is hydrogenated, the preferable weight average molecular weight is 10,000 or more and 1 million or less, more preferably 50,000 or more and 500,000 or less, and further preferably. It is 60,000 or more and 400,000 or less, and more preferably 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 by using gel permeation chromatography (GPC) by the method described in Examples described later.

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

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

Prepare several samples prepared by preparing a conjugated diene compound with the same composition and molecular weight as the polymer for which the hydrogenation rate is to be obtained at an arbitrary hydrogenation amount, and perform ¹ H-NMR measurement of the conjugated diene compound before and after hydrogenation. Measure. The reduction rate of olefinic protons before and after hydrogenation is obtained from the integrated ratio of all protons bound to the conjugated diene compound and the olefinic protons of the conjugated diene compound, and the reduction rate is calculated for each sample as the hydrogenation rate. A calibration curve is prepared from the integration 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, structural differences such as random structure and block structure can be observed as long as the ^{olefinic protons are observed as independent peaks by 1} H-NMR from the protons other than the olefinic protons and the amount of protons can be quantified. Therefore, if the sample has been analyzed for its monomer composition and molecular weight in advance, the hydrogenation rate can be easily measured even for a hydrogenated polymer having an unknown structure.

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. The conjugated diene compound is then extracted with acetone and the conjugated diene compound is vacuum dried. This is ^{used as a sample for 1} H-NMR measurement to measure the olefinic proton content of the conjugated diene compound.

By adding a large amount of methanol to the reaction solution containing the hydrogenation-conjugated diene compound after the hydrogenation reaction, the hydrogenation-conjugated diene compound is precipitated and recovered. The hydrogenated conjugated diene compound is then extracted with acetone and the hydrogenated conjugated diene compound is vacuum dried. This is ^{used as a sample for 1 1} H-NMR measurement to measure the hydrogenation rate.
¹ The conditions for 1 H-NMR measurement are described below.
Measuring equipment: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Measurement sample: Sample concentration before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400MHz
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 the conjugated diene block polymer is not particularly limited, but is preferably 5.0% or more and 100% or less, and is used as a hydrogenated material. In order to obtain sufficient 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 or more and 1 million or less is preferably 0.10 mass ppm or more and 30 mass ppm or less, and has a higher color tone. In order to obtain a product of 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 or less.

For the content of the insoluble gel component contained in the polymer of the present embodiment, a Buchner funnel equipped with 5A filter paper (for JIS P 3801 chemical analysis) is attached to a suction bottle having an internal volume of 2000 mL, and the pressure in the suction bottle is vacuum pumped. Measure using a filtration device that sucks under reduced pressure to 35 kPa. A solution prepared by dissolving 15 g of the polymer in 600 mL of toluene was suction-filtered, 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 surface was measured, and completely. After filtering, the filter paper is dried, the insoluble gel component remaining on the filter paper is dyed with a dyeing solution, and the number of insoluble gel components having a diameter of 1 mm or more is counted using a digital microscope (VHX-6000). It can be obtained 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 the product quality, and more preferably no insoluble gel component is confirmed after filtration. Is. The time required for filtration is preferably 0 to 60 seconds, more preferably 10 to 40 seconds, and even more preferably 20 to 30 seconds from the viewpoint of reducing the amount of insoluble loose gel that cannot be visually confirmed into the product. is there.

[Components of metal residue]
As described above, by reducing the amount of insoluble gel component generated to an extremely small amount, various metals that have conventionally been condensed together with the gel component and were difficult to separate from the product as insoluble metals can be specially selected for filters and the like. The present inventor has found that it can be separated from the polymer solution with high efficiency without using a simple device. Various metal components in the reduced state are oxidized by N-oxides to become water-soluble organic or inorganic salts, which can be separated into wastewater by being solubilized in treated water. By relying on such a mechanism, the present inventor assumes that any metal component in a reduced state is removed by the method of the present embodiment without being limited to a specific metal species.

The amount of metal residue remaining in the polymer is not particularly limited as long as it is within the above-mentioned content range, and the type, structure, and abundance ratio of the metal component are not particularly limited. Be done. That is, the metal can be one or more organic 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, a dispersant, etc. in the polymer manufacturing process, but if the metal is in a reduced state, the concentration in the polymer can be reduced. is there.

[Titanium metals]
The type of titanium metals is not particularly limited, but for example, crystalline titanium oxide such as rutile type, anatase type, and broccite type: amorphous titanium oxide, titanium hydroxide containing orthotitanium acid, metatitanium acid, etc .; water. Examples thereof include composite oxides of titanium and dissimilar metals such as titanium oxide and lithium titanate. Further, it may be an organic titanium complex bonded to various carboxylic acids, ligands such as amino acids, alcohols, ketones, aldehydes, and organic phosphoric acids by an arbitrary ratio of coordination numbers.

[Lithium metals]
The types of lithium metals are not particularly limited, and examples thereof include inorganic salts such as lithium hydroxide and lithium carbonate; and composite oxides of lithium and dissimilar metals such as lithium titanate. Further, it may be an organic lithium salt formed by neutralization or a chelating bond with various carboxylic acids, amino acids, alcohols, ketones, aldehydes, organic phosphoric acids and the like at an arbitrary ratio.

[Aluminum metals]
The types of aluminum metals are not particularly limited, and examples thereof include inorganic salts such as aluminum hydroxide and aluminum carbonate; and composite oxides of aluminum and dissimilar metals such as aluminum titanate. 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 types of nickel metals are not particularly limited, and examples thereof include inorganic salts such as nickel hydroxide and nickel oxide; and composite oxides of nickel and dissimilar 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 metal content]
Measurement is performed using inductively coupled plasma (ICP, Inductive Coupled Plasma, manufactured by Shimadzu Corporation, device name: ICPS-7510). First, the polymer is completely dissolved with sulfuric acid and nitric acid, an aqueous solution containing a metal component is sprayed into argon plasma, the intensity of the wavelength of the light peculiar to various metal elements emitted from the polymer is measured, and the calibration beam method is used. The amount of metal contained in the hydride conjugated diene polymer is determined.

[Method for producing polymer]
The method for producing the polymer of the present embodiment is a method for producing the polymer of the present embodiment, and has the following steps 1 to 4.
Step 1: Adjusting the polymer solution containing water and / or organic solvent and lithium and / or titanium Step 2: Step of contacting the polymer solution with the N-oxide compound Step 3: The polymer solution and acid Step 4: Mix the polymer solution to obtain a mixed solution Step 5: Remove 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 an aqueous solvent system or an organic solvent system, but an organic solvent system is preferable because the hydrogenation reaction can be directly carried out without going through the 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 manufacturing 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-based polymerization catalyst is mixed with a titanium compound. Examples thereof include a method of preparing a hydrogenated conjugated diene-based copolymer solution by performing a hydrogenation reaction under a catalyst composed of various reducing agents.

The polymer is not particularly limited as long as it is the polymer of the present embodiment, but specifically, it is a conjugated diene homopolymer having a molecular weight of 10,000 or more and 1 million or less, or a random mixture of a conjugated diene compound and an aromatic vinyl-based compound. , Tapered, block copolymers, etc. can be used, and hydrogenation can be added to the unsaturated double bond of these conjugated diene units.

The conjugated diene compound that can be used is not particularly limited, and is, 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 capable of copolymerizing with the conjugated diene compound is not particularly limited, and is, for example, styrene, α-methylstyrene, styrene substituted with an alkoxy group, 2-vinylpyridine, 4-vinylpyridine, vinylnaphthalene. , Vinylallyl compounds such as vinylnaphthalene substituted with an alkyl group can be used, preferably styrene and α-methylstyrene.

When a copolymer is produced by mixing a conjugated diene compound and a vinyl aromatic compound, 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 can be obtained, and when it is 95% by weight or less, the 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 carry out anionic polymerization using an organolithium compound as an initiator. As the organic lithium compound, specifically n-butyllithium, s-butyllithium and the like can be used. The amount of such an initiator used is generally used in the art, and can be freely adjusted depending on the molecular weight of the target polymer. A hydrogenated conjugated diene-based polymer can be produced by subjecting the obtained polymer solution to a hydrogenation reaction thereafter.

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, a cyclopentadienyl titanium halide or a cyclopenta. Dienyl (alkoxy) titanium dihalide, bis (cyclopentadienyl) titanium dihalide, bis (cyclopentadienyl) titanium dialkylate, bis (cyclopentadienyl) titanium diallylate and bis (cyclopentadienyl) titanium It is selected from dialkoxy compounds and can be used alone or in combination.

The titanium compound is preferably 0.01 to 20 mmol per 100 g of the conjugated diene polymer, and more preferably 0.05 to 5 mmol per 100 g of the polymer. When the amount of the titanium compound used is 0.01 mmol or more, it is preferable in terms of production from the viewpoint of the rate of hydrogenation reaction, and when it is 20 mmol or less, an unnecessary amount of catalyst is not generated, so that the economy is good. Since it is not necessary to remove the catalyst after the reaction, it is preferable to maintain the above range.

The reducing agent used together with the titanium compound is not particularly limited as long as it is a reducing agent generally used in the art, and examples thereof include an alkylaluminum compound, an alkylmagnesium compound, an organic lithium compound, and a metal hydride, and may be used alone. It can also be used in combination of multiple types.

The hydrogenation reaction using the titanium-based catalyst is not particularly limited, but is limited to International Patent Application No. 00/08069, US Pat. No. 4,501,857, 4,673,714, 4,980,421. It can be carried out by using the methods described in Nos. 5,753,778, 5,910,566, 6,020,439 and the like.

The hydrogenation reaction is carried out in an inert solvent, and the above-mentioned inert solvent means a solvent that does not react with any of the reactants of the polymerization or the hydrogenation reaction, specifically n-pentane, n-hexane, n-heptane, and so on. Alicyclic hydrocarbons such as n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cycloheptane; ethers such as diethyl ether and tetrahydrofuran can be mentioned and selected from these. It 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. When the polymer concentration is within the above range, the viscosity of the polymer solution can be adjusted to be easy to handle, and the productivity is improved, which is preferable.

On the other hand, in the hydrogenation reaction, the polymer solution is maintained at a constant temperature in an atmosphere of an inert gas such as hydrogen, helium, argon, or nitrogen, and then a hydrogenation catalyst is added in a stirred or unstirred state to add hydrogen gas. It is preferable to inject at a constant pressure. Further, 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 the residual metal from the polymer solution, for example, the conjugated diene polymer solution in which the hydrogenation reaction has been completed as described above, the steps 2 and 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 its solution. More specifically, for example, a hydrogenated conjugated diene-based polymer solution, a non-carboxylic acid organic compound, and an N-oxide compound are added sequentially or in combination. Alternatively, it is a step of adding the N-oxide compound to the polymer solution alone or as an aqueous solution.

The non-acidic organic compound may be mixed and dissolved with N-oxide for the purpose of increasing the solubility of the N-oxide compound in the polymer solution, or may be added separately. When N-oxide is water-soluble, it may be added to the polymer solution as an aqueous solution. Further, when the N-oxide compound can be handled as 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-oxide compound of the polymerization solvent is N. -It may be added to the polymer solution as an oxide compound solution.

When a non-carboxylic acidic organic compound is used in the present embodiment, at least one or more non-carboxylic acidic 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 it.

(Non-carboxylic acid organic compound)
Non-carboxylic acidic organic compounds refer to compounds that do not have a carboxyl group in their 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 at the same time as the N-oxide compound, the carboxyl group in the molecule associates with the N-oxide between the molecules. This is because the activity is significantly reduced. The non-carboxylic acidic organic compound is not particularly limited as long as it is a compound having no carboxyl group, but has a functional group other than an ester group, a ketone group, an alcohol group, an acid anhydride group, and an amino group in the molecule. You may. The non-carboxylic acidic 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 either one of the conditions of 0 or more, and it is more preferable to satisfy both properties in order to maintain the activity of the N-oxaside compound. The non-acidic organic compound is not particularly limited, and examples thereof include the following.

(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. -Butandiol, 1,4-butanediol, isobutanol, tert-butanol, pentanol, isopentanol, neopentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, cinnamyl alcohol, 1 -Dodecanol, 4-methoxybenzyl alcohol, perylyl alcohol, p-kumalyl alcohol, 2-phenylethanol, 1-undecanol, 1-phenylethanol, cumyl alcohol, benzyl alcohol, 1-nonanol, 2-hydroxybenzyl alcohol, 1-O-hexadecyl-L-glycerol, synapyl alcohol, 2-phenyl-1-propanol, 2-methyl-2-propen-1-ol, crotyl alcohol, (Z) -3-hexene-1-ol, 1 -Icosanol, 1-triacon ethanol, 1-phenyl-2-methyl-2-propanol, vanillyl alcohol, furfuryl alcohol, 1-hexadecanol, 10-undecene-1-ol, 1-octadecanol, allyl alcohol , Diacetone alcohol, caffe oil 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, reno Examples include rail alcohol, hydroxymethyl mexyletine alcohol, and retinol.

(Esters)
Examples of 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, phenylcaprylate, methyl pelargonate, ethyl pelargonate, propyl pelargone, butyl pelargone, hexyl pelargone, phenyl pelargone, methyl caprate, ethyl caprate, propyl caprate, butyl caprice, caprin Hexyl acid, 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 margarate, ethyl margarate, propyl margarate, butyl margarate, hexyl margarate, margarine Phenyl acid, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, hexyl stearate, phenyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, methyl crotonate , Ethyl crotonate, propyl crotonate, butyl crotonate, hexyl crotonate, phenyl crotonate, methyl balmitreate, ethyl balmitreate, propyl balmitreate, butyl balmitreate, hexyl balmitreate, phenyl balmitreate, methyl oleate, olein Ethyl acidate, propyl oleate, buice oleate Chill, hexyl oleate, phenyl oleate, methyl buxate, ethyl buxate, propyl bactate, butyl buxenate, hexyl buxenate, phenyl buxenate, methyl linoleic acid, ethyl linoleate, propyl linoleate, butyl linoleate, Hexyl linoleate, phenyl linolenate, methyl linolenate, ethyl linolenate, propyl linolenate, butyl linolenate, hexyl linolenate, phenyl linolenate, methyl stearidonic acid, ethyl stearidonic acid, propyl stearidonic acid, butyl stearidonic acid, stearidonic acid Hexil, 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 trimeritate, triethyl trimeritate, methyl 2-ketopropionate, methyl 2-ketobutyrate, methyl acetoacetate, lactic acid Examples thereof include methyl, 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, Dimedon can be mentioned.

(Aldehydes)
Examples of aldehydes include acetaldehyde, propionaldehyde, isobutylaldehyde, benzaldehyde, pivalaldehyde, glyoxal, butylaldehyde, 3,3-dimethylbutylaldehyde, isobarrelaldehyde, heptanal, hexanal, barrelaldehyde, crotonaldehyde, decanal, and the like. Metachlorine, n-octanal, dodecanal, 3-methyl-2-butenal, tetradecanal, achlorine, glutaaldehyde, bromal, chloral, cis-4-heptenal, cyclohexanecarboxyaldehyde, trans, cis-2,6-nonaaldi Examples include aldehyde and 3,7-citronellal.

(Acid anhydrides)
Examples of acid anhydrides include acetic anhydride, succinic anhydride, 2,2-dimethylsucci anhydride, butyl succi anhydride, decyl succi anhydride, n-octyl succi anhydride, and dodecyl succi anhydride. , Itaconic Acid anhydride, Allyl succinic anhydride, Hexadecyl succinic anhydride, Octadecyl succinic anhydride, meso-butane-1,2,3,4-tetracarboxylic acid anhydride, (2-Methyl-2- Propenyl) succinic anhydride, 2-butene-1-ylsuccinic anhydride, cis-1,2-cyclohexanedicarboxylic acid anhydride, trans-1,2-cyclohexanedicarboxylic acid anhydride, 2-hexene-1-ylsuccinic acid Anhydrous, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, 2-octenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, O-acetyl-apple acid anhydride, 1 , 2,3,4-Cyclopentanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, 2-dodecene-1-ylsuccinic anhydride, tetrafluorosuccinic anhydride , Caronic anhydride, (+)-diacetyl-L-tartrate anhydride, (-)-diacetyl-D-tartrate anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,2, 3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride Acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, bicyclo [2,2,2] octo-7-en-2, 3,5,6-Tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, phenylsuccinic anhydride, 3 , 4-thiophene dicarboxylic acid anhydride, het acid anhydride, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, Phthalic anhydride, 4-fluorophthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,2-naphthalic anhydride, 4,4'-biphthalic anhydride, 4-methylphthalic anhydride, 3 -Methyl phthalic anhydride, pyromellitic anhydride, 4-tert-butyl phthalic anhydride, 3,3', 4,4'-Benzophenone tetracarboxylic dianhydride, 4- (1-propynyl) phthalic anhydride, 4,4'-oxydiphthalic acid anhydride, 3,4'-oxydiphthalic acid anhydride, 4,4-( Ethine-1,2-diyl) diphthalic anhydride, (1β, 4β) -bicyclo [2,2,1] hepta-5-ene-2α, 3α-dicarboxylic acid anhydride, valeric acid anhydride, pentafluoropropion Acid anhydrides, [3- (trimethoxysilyl) propyl] succinic anhydrides can be mentioned.

(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-methylpiperidin, piperidone, N-methylpiperidone, piperazin, N-methylpiperidin, morpholin, N-methylmorpholin, 2,2,6 , 6-Tetramethyl N-methylmorpholin, pyrrol, N-methylpyrol, pyridine, α-picolin, pyridazine, pyrimidine, 1,3,5-triazine, imidazole, N-methylimidazole, pyrazole, N-methylpyrazole, oxazole , Thiazol, azepine, N-methylazepine, imidazoline, N-methylimidazoline, pyrazine, thiazine, indol, N-methylindole, isoindole, N-methylisoindole, benzoimidazole, purine, N-methylpurine, quinoline, isoquinolin , Kinoxalin, Synnoline, Pteridine, Carbazole, N-Methylcarbazole, 2,6-Lutidine, 3,5-Lutidine, Amidin, Guanidin, Methyleneamine, acetonitrile, benzonitrile, Nicotin, Nicotic 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 themselves by heating or the like. Is more preferable, and a liquid alone at normal temperature and atmospheric pressure is more preferable.

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

(N-oxide compound)
The N- oxide compounds, in the molecule N ⁺ -O - ^(Another notation N = O, N → O) , or a group of compounds having the functional group represented by N-O ·, primary amine, secondary It refers to 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 general of the following formulas (1), (2), formulas (3) and (4). It can be expressed by an expression.

In formula (1), R ₁ , R ₂ , and R ₃ are aliphatic chain substituents having 30 or less carbon atoms and containing a substituent composed of an element selected from H, O, N, S, and P. , aromaticity cyclic substituents including aliphatic cyclic substituents or heterocycle, or heteroaryl aliphatic cyclic _{substituent, R 1, R 2, R} 3 can be identical or different, may be different. R1 and R2 bonded to the N-oxide group together, bond to the N atom of the N-oxide group in a double bond, and are substituted with an element selected from H, O, N, S, and P. It may be an aliphatic chain substituent containing a group and having 30 or less carbon atoms, an aliphatic cyclic substituent, or a heteroaliphatic cyclic substituent.

In addition, 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 in a triple bond to be selected from H, O, N, S and P. It may be an aliphatic chain substituent having 30 or less carbon atoms and containing a substituent composed of an element.

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

Further, the rings B and C may have one or a plurality of the same or different substituents composed of elements selected from H, O, N, S, and P. Further, the ring B and the ring C may have different ring structures from each other, and may have the same ring structure. Further, the ring B and the ring C are at positions different from the positions where they are bonded to the ring A, respectively, and are an aromatic ring, an aliphatic ring, and a hetero, which are independently composed of elements selected from H, O, N, S, and P. A fused ring may be formed with an aromatic ring or a heteroaliphatic ring.

In the formula, R ₄ contains an aliphatic chain substituent having 30 or less carbon atoms, an aliphatic cyclic substituent or a heterocycle containing a substituent composed of an element selected from H, O, N, S and P. It is an aromatic cyclic substituent or a heteroaliphatic cyclic substituent, and the bond valence of the N atom of the N-oxide group satisfies the tetravalence only with the atom constituting the ring A and the O atom of the N-oxide group. The cases do not necessarily have to be combined.

In formula (3), R ₅ and R ₆ are aliphatic chain substituents having 30 or less carbon atoms and aliphatic cyclic compounds containing a substituent composed of an element selected from H, O, N, S, and P. It is an aromatic 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, which is composed of an element selected from H, C, O, N, and S, and rings E and F are It is an aromatic ring, an aliphatic ring, a heteroaromatic ring, or a heteroaliphatic ring having 3 to 10 ring members, which is 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 arbitrary positions to form a fused ring. Ring A does not necessarily have to form a fused ring with ring B and ring C, and may be a single heteroaliphatic ring. Further, when the ring D forms a fused ring with the ring E, the ring F does not necessarily have to be bonded. Further, the ring D may have one or a plurality of the same or different substituents composed of elements selected from H, O, N, S, and P.

Further, the rings E and F may have one or a plurality of the same or different substituents composed of elements selected from H, O, N, S, and P. Further, the ring E and the ring F may have different ring structures from each other, and may have the same ring structure. Further, the ring E and the ring F are positions different from the positions where they are bonded to the ring D, respectively, and are an aromatic ring, an aliphatic ring, and a hetero ring which are independently composed of elements selected from H, O, N, S, and P. A fused ring may be formed with an aromatic ring or a heteroaliphatic ring.

The N-oxide compound is not particularly limited as long as it has a structure obtained by oxidizing the nitrogen-containing compound group shown below with an oxidizing agent such as hydrogen peroxide, persulfate, 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, or may be a hydrate. Examples of nitrogen-containing compounds having a matrix structure of N-oxide compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, ethylenediamine, hexamethylenediamine, hexamethyleneimine, N-methylhexamethyleneimine, triethylamine, and N-cyclohexyl. Amine, N, N-cyclohexylmethylamine, N, N-dimethyldodecylamine, aniline, N, N-dimethylaniline, piperidine, N-methylpiperidin, piperidone, N-methylpiperidone, piperazin, N-methylpiperidin, morpholin, N -Methylmorpholin, 2,2,6,6-tetramethyl N-methylmorpholin, 2,2,6,6-tetramethyl-1-piperidin, 8-azabicyclo [3.2.1] octane, 7-azabicyclo [ 2.2.1] Heptane, 2-azaadamantan, 1-methyl-2-azaadamantan, pyrrol, N-methylpyrrole, pyridine, α-picolin, pyridazine, pyrimidine, 1,3,5-triazine, imidazole, N -Methylimidazole, pyrazole, N-methylpyrazole, oxazole, thiazole, azepine, N-methylazepine, imidazoline, N-methylimidazoline, pyrazine, thiazine, indol, N-methylindole, isoindole, N-methylisoindole, benzo Imidazole, purine, N-methylpurine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, carbazole, N-methylcarbazole, 2,6-lutidine, 3,5-lutidine, amidine, guanidine, methyleneamine, acetonitrile, benzonitrile, Examples include nicotine, nicotinic acid, and nicotinic acid amide.

The specific N-oxide compound is not particularly limited as long as it is generally used, but is 3-acetylpyridine N-oxide, 2-aminopyridine N-oxide, pyridine N-oxide, 4-chloro. Pylinate 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-phenylnitron, N-tert-butyl-α- (4-pyridyl-1-oxide) nitron, 5,5-dimethyl-1-pyrrolin N-oxide, quinoline N-oxide, 4- (hydroxyamino) ) Kinolin N-oxide, 2-hydroxypyridine N-oxide, 3-hydroxypyridine N-oxide, isonicotinic acid N-oxide, isoquinolin 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-methylmorpholin N-oxide, N-methylmorpholin N-oxide 2-methylpyridine N-oxide, 3-Methylpyridine N-oxide, 4-methylpyridine N-oxide, nicotine amide N-oxide, nicotinic 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-pyrrolin N-oxide, trimethylamine N-oxide, 2,2,6,6-tetramethyl-1-piperidin N -Oxyl, [8-azabicyclo [3.2.1] octane N-oxyl], [7-azabicyclo [2.2.1] heptane N-oxyl], 2-azaadamantan N-oxyl, 1-methyl-2 -Azaadamantan 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 effectively used.

In the present embodiment, the order in which the non-acidic organic compound and the N-oxide compound are added to the polymer solution is not particularly limited, but the N-oxide compound may be added after the non-acidic organic compound is 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 the 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. Is more preferable. In particular, when the metal residue is lithium or titanium, the molar ratio is more preferably in the above range.

When N-oxide is added to the polymer solution as an aqueous solution, the amount of water to be 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, the metal residue contained in the polymer solution tends to be easily removed, and the amount of wastewater tends to be reduced.

[Step 3]
In step 3, the polymer solution obtained in step 2 and the acid are mixed. Here, the acid may be an organic acid or an inorganic acid, and indicates an aqueous solution pH of 1 or more and less than 7 when an acid compound and water are mixed to form an aqueous solution. 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 of two or more. If the pH is lower than 4 when the solution is made into an aqueous solution and it is expected that an excessive burden will be applied to the manufacturing equipment, the pH should be set to less than 7 with a basic salt of an alkali metal or an alkaline earth metal in advance. It may be a mixture of an organic acid and an organic acid salt prepared in 4 or more.

In the present embodiment, the structure of the organic acid compound is not particularly limited, and a generally known organic acid 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, glutanic acid, ascorbic acid, formic acid, acetic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, Examples thereof include glycine, alanine, cystine, serine, inositol trisphosphate, phytic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid.

The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.

In step 3, the molar ratio of the 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 the acid in 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 a method of preparing an aqueous solution of the acid compound in advance and mixing it with the polymer solution, or a method of adding the acid compound after mixing the polymer solution and water. From the viewpoint of simplifying the process, it is preferable to add an aqueous solution of the 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 or more and 20 volume times that of the polymer solution. It is preferable to adjust so that the range is as follows.

[Step 4]
In step 3, the mode of mixing the polymer solution with the N-oxide compound and the aqueous solution of the acid is not particularly limited, but for example, the meshing as described in FIG. 1 (cited from JP-A-6-136034). 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 decalcification operation. The meshing structure of the rotary disperser is a structure in which a rotor having a comb tooth or a hole and a stator are meshed with each other. The mixture of the polymerization solution and the aqueous solution charged into the rotary disperser receives centrifugal force due to the rotation of the rotor at high speed, and flows through the gap between the rotor and the stator to the discharge port. During this period, a shearing force acts in a minute gap between the rotor and the stator to achieve uniform dispersion.

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 ), and more preferably 1 × 10 ⁵ (kw / m 3). 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 at the time of mixing. V (m ³ ) is the space volume of the mixing portion in the rotary disperser, and is the space volume of the portion that applies a shearing force to the solution. Further, the peripheral speed (2πr · n) is set to 5 (m / s) or more, preferably 7 (m / s), and more preferably 10 (m / s). Here, r (m) is the radius of the outermost teeth of the rotor in the rotation disperser, and n (s ^-1 ) is the rotation speed of the rotor in the rotation disperser. By operating the rotary disperser under the above conditions, the polymer solution can be efficiently mixed with water, an acid compound, and an organic acid, and a good metal with a short average residence time of 0.01 to 10 (s). There is a tendency to obtain removal efficiency.

[Step 5]
Step 5 is a step of removing (separating) the aqueous phase from the mixed solution and further desolving the purified polymer solution to obtain a polymer. The method for separating water in step 5 is not particularly limited as long as it is generally used in the art, but for example, a mixed solution consisting of a polymer solution and an aqueous layer is statically separated, centrifuged, and countercurrent. Examples thereof include a method of removing the aqueous phase by extraction or the like. The desolvation treatment is not particularly limited as long as it is generally used, but for example, a method of obtaining a polymer crumb by steam stripping, or direct desolvation using a drum dryer or a devolatilization extruder. Examples thereof include a method of obtaining a polymer by treatment.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

[Manufacturing Example 1]
400 g of a 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 catalyzed by n-BuLi. 2800 g of the containing cyclohexane solution was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Then, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride were added, and the polymer solution was hydrogenated by pressurizing with hydrogen of ^{10 kg / cm 2 to carry out a hydrogenation reaction.} Got As a result of NMR analysis of the polymer (polymer) hydrogenated in this way, it was confirmed that 98% or more of the double bonds in the polybutadiene block were hydrogenated. As a result of measuring the amount of metal contained in the obtained polymer through elemental analysis using inductively coupled plasma (ICP), Ti residue: 102 ppm, Li residue: 100 ppm, Al residue: 101 ppm. It was.

[Manufacturing Example 2]
400 g of a 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 catalyzed by n-BuLi. 2800 g of the containing cyclohexane solution was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Then, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride were added, and the polymer solution was hydrogenated by pressurizing with hydrogen of ^{10 kg / cm 2 to carry out a hydrogenation reaction.} Got As a result of NMR analysis of the polymer (polymer) hydrogenated in this way, it was confirmed that 80% of the double bonds in the polybutadiene block were hydrogenated. As a result of measuring the amount of metal contained in the obtained polymer through elemental analysis using inductively coupled plasma (ICP), Ti residue: 100 ppm, Li residue: 102 ppm, Al residue: 100 ppm. It was.

[Manufacturing Example 3]
400 g of a 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 catalyzed by n-BuLi. 2800 g of the containing cyclohexane solution was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Then, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride were added, and the polymer solution was hydrogenated by pressurizing with hydrogen of ^{10 kg / cm 2 to carry out a hydrogenation reaction.} Got As a result of NMR analysis of the polymer (polymer) hydrogenated in this way, it was confirmed that 30% of the double bonds in the polybutadiene block were hydrogenated. As a result of measuring the amount of metal contained in the obtained polymer through elemental analysis using inductively coupled plasma (ICP), Ti residue: 103 ppm, Li residue: 100 ppm, Al residue: 101 ppm. It was.

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

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

[Manufacturing 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 catalyzed by n-BuLi. 2800 g of the containing cyclohexane solution was placed in a 5 liter autoclave reactor and heated to 60 ° C. with stirring at 400 rpm. Then, 1.5 mmol of triethylaluminum and 0.8 mmol of bis (cyclopentadienyl) titanium dichloride were added, and the polymer solution was hydrogenated by pressurizing with hydrogen of ^{10 kg / cm 2 to carry out a hydrogenation reaction.} Got As a result of NMR analysis of the polymer (polymer) hydrogenated in this way, it was confirmed that 80% of the double bonds in the polybutadiene block were hydrogenated. As a result of measuring the amount of metal contained in the obtained polymer through elemental analysis using inductively coupled plasma (ICP), 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 (metal amount) in terms of metal atom contained in the inductively coupled diene polymer obtained in Examples or Comparative Examples The inductively coupled diene polymer obtained in Examples or Comparative Examples described later. The amount of metal contained therein was measured using inductively coupled plasma (ICP, Inductively Coupled Plasma, manufactured by Shimadzu Corporation, device name: ICPS-7510). First, the polymer is completely dissolved with sulfuric acid and nitric acid, an aqueous solution containing a metal component is sprayed into argon plasma, the intensity of the wavelength of the light peculiar to various metal elements emitted from the polymer is measured, and the calibration beam method is used. The amount of metal contained in the hydride conjugated diene polymer was determined. Specifically, the metal amounts of Li, Ti, and Al were determined.

[Amount of insoluble gel component (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 having an internal volume of 2000 mL, and the pressure inside the suction bottle was reduced to 35 kPa using a vacuum pump. Using this filtration device, a solution in which 15 g of the polymer is dissolved in 600 ml of toluene is suction-filtered, and the time from the start of filtration until the liquid level gradually drops and the surface of the filter paper is exposed from the liquid surface. It was measured. After being completely filtered, the filter paper was dried, and the insoluble gel component remaining on the filter paper was stained with a dyeing solution. Using a digital microscope (VHX-6000 manufactured by KEYENCE), the number of insoluble gel components having a diameter of 1 mm or more was counted.

[Color tone]
The hydrogenated conjugated diene polymer obtained in Examples and Comparative Examples described later was compression-molded to prepare a sheet having a thickness of 2 mm, and the b value of the obtained sheet was measured by a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.). It was measured using ZE-2000). It was evaluated that the larger the b value, the stronger the yellowish color of the molded product of the hydrogenated conjugated diene polymer and the worse the color tone.
[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 times mol of ethanol with respect to the metal residue was added, and 2 times mol of malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in twice the volume of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and 2 times the molar amount of citric acid was added to the metal residue. An aqueous solution dissolved in twice the volume of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and then 2 times the molar amount of sulfuric acid aqueous solution was added to the metal residue. A diluted aqueous solution was added to a volume of water, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and 2 times mol of malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in twice the volume of water is added to the solution, and the mixture is mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure. A mixture was obtained. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and 2 times mol of citric acid was added to the metal residue. An aqueous solution dissolved in twice the volume of water is added to the solution, and the mixture is mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure. A mixture was obtained. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol was added to the metal residue, and then 2 times mol of sulfuric acid aqueous solution was added to the metal residue. A diluted aqueous solution was added to a volume of water, and the mixture was mixed with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having an meshing structure at 60 ° C. and 7600 rpm for 1 second (sec) to obtain a mixed solution. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and 2 times mol of malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in twice the volume of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.
[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and 2 times the molar amount of citric acid was added to the metal residue. An aqueous solution dissolved in twice the volume of water was added to the solution, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and 2 times mol of malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in twice the volume of water is added to the solution, and the mixture is mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure. A mixture was obtained. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and 2 times mol of malic acid was polymerized with respect to the metal residue. An aqueous solution dissolved in twice the volume of water is added to the solution, and the mixture is mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having a meshing structure. A mixture was obtained. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and then 2 times the molar amount of sulfuric acid aqueous solution was added to the metal residue. A diluted aqueous solution was added to a volume of water, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and then 2 times the molar amount of sulfuric acid aqueous solution was added to the metal residue. A diluted aqueous solution was added to a volume of water, and the mixture was vigorously stirred at 60 ° C. for 10 minutes in a mixer equipped with a stirrer. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and then 2 times the molar amount of sulfuric acid aqueous solution was added to the metal residue. A diluted aqueous solution was added to a volume of water, and the mixture was mixed with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having an meshing structure at 60 ° C. and 7600 rpm for 1 second (sec) to obtain a mixed solution. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times the molar amount of ethanol with respect to the metal residue was added, and then 2 times the molar amount with respect to the metal residue. An aqueous solution obtained by diluting an aqueous solution of sulfuric acid in a double volume of water is added, and the mixture is mixed for 1 second (sec) at 60 ° C. and 7600 rpm by a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having an meshing structure. Obtained liquid. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and then 2 times mol of an aqueous apple acid solution was added to the metal residue. A diluted aqueous solution was added to double volume of water, and the mixture was mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having an meshing structure to obtain a mixed solution. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and then 2 times mol of an aqueous apple acid solution was added to the metal residue. A diluted aqueous solution was added to double volume of water, and the mixture was mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having an meshing structure to obtain a mixed solution. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 times mol of ethanol with respect to the metal residue was added, and then 2 times mol of an aqueous apple acid solution was added to the metal residue. A diluted aqueous solution was added to double volume of water, and the mixture was mixed for 1 second (sec) at 60 ° C. and 7600 rpm with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) having an meshing structure to obtain a mixed solution. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

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

[Comparative Example 1]
The polymer solution obtained in Production Example 1, 30% hydrogen peroxide solution that is 2 volumes of the polymer solution, and malic acid that is 2 times the molar amount of titanium are mixed in a mixer with a stirrer. The mixture was vigorously stirred at ° C. for 10 minutes. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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]
The polymer solution obtained in Production Example 2, 30% hydrogen peroxide solution that is 2 volumes of the polymer solution, and malic acid that is 2 times the molar amount of titanium are mixed in a mixer with a stirrer. The mixture was vigorously stirred at ° C. for 10 minutes. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 that is 2 volumes of the polymer solution, and malic acid that is 2 times the molar amount of titanium are mixed in a mixer with a stirrer. The mixture was vigorously stirred at ° C. for 10 minutes. Then, the obtained mixed solution was allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 prepared by dissolving 2 times mol of malic acid in 2 times the volume of water with respect to the metal residue is added to have an meshing structure. A mixed solution was obtained by mixing with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) at 60 ° C. and 7600 rpm for 1 second (sec). At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 prepared by dissolving 2 times mol of malic acid in 2 times the volume of water with respect to the metal residue is added to have an meshing structure. A mixed solution was obtained by mixing with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) at 60 ° C. and 7600 rpm for 1 second (sec). At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

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

[Comparative Example 6]
To the polymer solution obtained in Production Example 3, an aqueous solution prepared by dissolving 2 times mol of malic acid in 2 times the volume of water with respect to the metal residue is added to have an meshing structure. A mixed solution was obtained by mixing with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) at 60 ° C. and 7600 rpm for 1 second (sec). At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

[Measurement of metal content]
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 prepared by dissolving 2 times mol of malic acid in 2 times the volume of water with respect to the metal residue is added to have an meshing structure. A mixed solution was obtained by mixing with a rotary disperser (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) at 60 ° C. and 7600 rpm for 1 second (sec). At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. The separated state was good. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a solid polymer.

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

Claims (7)

A polymer containing a conjugated diene compound unit or a polymer containing a polymer block containing a conjugated diene compound unit and having a weight average molecular weight of 10,000 or more and 1 million or less has a metal content of metal. , 0.10 mass ppm or more and 30 mass ppm or less, which is a method for producing a conjugated diene-based block polymer.
It has the following steps 1-5.
Method for producing polymer.
Step 1: Prepare a polymer solution containing water and / or an organic solvent and lithium and / or titanium Step 2: Contact the polymer solution with the N-oxide compound Step 3: The polymer solution and acid Step 4: Mixing the polymer solution Step 5: Removing water and / or organic solvent from the polymer solution In step 2, the molar ratio of the N-oxide compound to lithium and / or titanium is 0.01 or more and 10 or less.
The method for producing a polymer according to claim 1. In step 3, the molar ratio of the acid to lithium and / or titanium is 0.1 or more and 50 or less.
The method for producing a polymer according to claim 1 or 2. In the conjugated diene-based block polymer, the content of the insoluble gel component satisfies the following conditions.
The method for producing a polymer according to any one of claims 1 to 3:
(Content of insoluble gel component)
A Buchner funnel 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 inside the suction bottle was measured using a filtration device that sucked down to 35 kPa using a vacuum pump. A solution prepared by dissolving 15 g of the polymer in 600 mL of toluene is suction-filtered, and after being completely filtered, the filter paper is dried, and the insoluble gel component remaining on the filter paper is dyed with a dyeing solution to make it insoluble with a diameter of 1 mm or more. The number of visible gels visually recognized on the filter paper, which was obtained by measuring the number of gel components, is 2 or less. The polymer is the conjugated diene-based block polymer.
The conjugated diene-based block polymer further contains a polymer block containing a vinyl aromatic hydrocarbon unit.
The method for producing a polymer according to any one of claims 1 to 4. In the conjugated diene-based block polymer, the total hydrogenation rate H of the double bond derived from the conjugated diene compound is 5.0% or more and 100% or less.
The method for producing a polymer according to any one of claims 1 to 5. The metal is one or more organic or inorganic salts selected from the group consisting of titanium metals, lithium metals, aluminum metals, and nickel metals.
The method for producing a polymer according to any one of claims 1 to 6.

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